CA2393175C - Bridged metallocene compounds as olefin-polymerization catalysts - Google Patents
Bridged metallocene compounds as olefin-polymerization catalysts Download PDFInfo
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- CA2393175C CA2393175C CA002393175A CA2393175A CA2393175C CA 2393175 C CA2393175 C CA 2393175C CA 002393175 A CA002393175 A CA 002393175A CA 2393175 A CA2393175 A CA 2393175A CA 2393175 C CA2393175 C CA 2393175C
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- formula
- reaction
- halogen
- hydrocarbyl group
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- 239000002685 polymerization catalyst Substances 0.000 title description 4
- -1 indenyl-cyclopentadienyl groups Chemical group 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 114
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 90
- 239000000203 mixture Substances 0.000 claims description 77
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 58
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 28
- 125000005842 heteroatom Chemical group 0.000 claims description 25
- 229920006395 saturated elastomer Polymers 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 23
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 21
- 238000005755 formation reaction Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 16
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- YIAPLDFPUUJILH-UHFFFAOYSA-N indan-1-ol Chemical class C1=CC=C2C(O)CCC2=C1 YIAPLDFPUUJILH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims description 7
- DKLQZDIAQKGVTA-UHFFFAOYSA-N 4,7-dimethyl-1h-indene Chemical compound CC1=CC=C(C)C2=C1CC=C2 DKLQZDIAQKGVTA-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000004210 ether based solvent Substances 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910020667 PBr3 Inorganic materials 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052735 hafnium Chemical group 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003997 cyclic ketones Chemical class 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- WCYBYZBPWZTMDW-UHFFFAOYSA-N dibutylazanide Chemical compound CCCC[N-]CCCC WCYBYZBPWZTMDW-UHFFFAOYSA-N 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- NIXOIRLDFIPNLJ-UHFFFAOYSA-M magnesium;benzene;bromide Chemical compound [Mg+2].[Br-].C1=CC=[C-]C=C1 NIXOIRLDFIPNLJ-UHFFFAOYSA-M 0.000 claims description 2
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000005425 toluyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims 6
- 239000012024 dehydrating agents Substances 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 150000001639 boron compounds Chemical class 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910000103 lithium hydride Inorganic materials 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229950010765 pivalate Drugs 0.000 claims 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims 1
- 235000013350 formula milk Nutrition 0.000 description 58
- 239000000243 solution Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000306 component Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 description 23
- 235000011152 sodium sulphate Nutrition 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 19
- 239000007832 Na2SO4 Substances 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- 239000000284 extract Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 235000010210 aluminium Nutrition 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 12
- 229940093470 ethylene Drugs 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 229940095050 propylene Drugs 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 8
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 150000008040 ionic compounds Chemical class 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- PVBRHCLTAGGWNB-UHFFFAOYSA-N 2-(1h-inden-1-yl)-1-methyl-4-methylideneindene Chemical compound C1=CC2=CC=CC=C2C1C1=C(C)C2=CC=CC(=C)C2=C1 PVBRHCLTAGGWNB-UHFFFAOYSA-N 0.000 description 4
- XVTQSYKCADSUHN-UHFFFAOYSA-N 3-methyl-2,3-dihydroinden-1-one Chemical compound C1=CC=C2C(C)CC(=O)C2=C1 XVTQSYKCADSUHN-UHFFFAOYSA-N 0.000 description 4
- JTUTZTVFJIHGGX-UHFFFAOYSA-N 4-methyl-2,3-dihydro-1h-inden-1-ol Chemical compound CC1=CC=CC2=C1CCC2O JTUTZTVFJIHGGX-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical group [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- LNQVCJCCOORXHZ-UHFFFAOYSA-N 3-methyl-2,3-dihydro-1h-inden-1-ol Chemical compound C1=CC=C2C(C)CC(O)C2=C1 LNQVCJCCOORXHZ-UHFFFAOYSA-N 0.000 description 3
- GCZQTQUHBZZQAC-UHFFFAOYSA-N 4,7-dimethyl-2,3-dihydroinden-1-one Chemical compound CC1=CC=C(C)C2=C1CCC2=O GCZQTQUHBZZQAC-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229940076134 benzene Drugs 0.000 description 3
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- NGTBNLRJDVKUKE-UHFFFAOYSA-N ethyl 3-hydroxy-1-methyl-2,3-dihydro-1h-indene-4-carboxylate Chemical compound CCOC(=O)C1=CC=CC2=C1C(O)CC2C NGTBNLRJDVKUKE-UHFFFAOYSA-N 0.000 description 3
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Chemical group 0.000 description 3
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- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
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- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical group 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
- C07C13/465—Indenes; Completely or partially hydrogenated indenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S526/943—Polymerization with metallocene catalysts
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Abstract
The present invention relates to metallocene compounds consisting of indenyl-cyclopentadienyl groups non-sym-metrically joined by a bivalent radical. Said compounds can be conveniently used as components of catalysts for the polymerization of olefins.
Description
BRIDGED METALLOCENE COMPOUNDS AS OLEFIN-POLYMERIZATION CATALYSTS
The present invention relates to bridged metallo-cene compounds, the corresponding ligands, a process for their preparation and the use of said compounds as components of catalysts for the polymerization of ole-fins.
More specifically, the invention relates to met-allocene compounds consisting of indenyl-cyclopentadienyl groups, non-symmetrically joined by a bivalent radical.
It is known that metallocene compounds can be used in various reactions of industrial interest.
For example, chiral, stereo rigid metallocene compounds consisting of two bridged indenyl groups and a metal such as zirconium, are known and used as com-ponents of catalysts for the polymerization of olefins and, in particular, for the preparation of stereo-regular polyolefins.
In these metallocenes, the indenyl groups are joined by means of bivalent radicals which have two or more carbon atoms, such as -(CH2)2 groups or with atoms different from carbon.
These radicals are generally bound in different positions relating to the ring with five carbon atoms of both indenyl groups, as described in patent appli-cations EP-A-485,823, EP-A-372,414, WO 94/11406.
Metallocenes are also known, whose indenyl groups are joined by means of bivalent radicals bound in po-sition 4 of the ring with six carbon atoms of both in-denyl groups, as described in patent applications EP
693 502, WO 96/38458.
New metallocene compounds have now been found in which the bivalent radical is bound to the ring with five carbon atoms of a cyclopentadienyl, indenyl, fluorenyl group and to the ring with six carbon atoms of an indenyl group, which can be conveniently used as components of catalysts for the polymerization of ole-f ins .
An object of present invention relates, in par-ticular, to metallocene compounds having general for-mula ( I ) :
R,, t X.
R7 R3 NI~
X, R, RI
~I) wherein:
- R1 and R2 can independently occupy any of the free positions of the indene group;
- R1, R2, R3, R4, R5, R6, R-7 and R8 independently rep-resent hydrogen, halogen, preferably F, Cl or Br, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C->o hydrocarbyl group substituted with one or more halogen atoms, or a CI-C=o hydro-carbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, preferably Si, 0, N, S, P; in addition, any two, or both pairs, of the substituents R3, R4, R; and R5r adjacent to each other, are joined to each other to form a saturated or unsaturated C4-C20 cy-clic structure, said structure optionally contain-ing one or more of the heteroatoms specified above;
- M represents titanium, zirconium or hafnium; and - X1 and X2 each independently represent a group of an anionic nature bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
The present invention relates to bridged metallo-cene compounds, the corresponding ligands, a process for their preparation and the use of said compounds as components of catalysts for the polymerization of ole-fins.
More specifically, the invention relates to met-allocene compounds consisting of indenyl-cyclopentadienyl groups, non-symmetrically joined by a bivalent radical.
It is known that metallocene compounds can be used in various reactions of industrial interest.
For example, chiral, stereo rigid metallocene compounds consisting of two bridged indenyl groups and a metal such as zirconium, are known and used as com-ponents of catalysts for the polymerization of olefins and, in particular, for the preparation of stereo-regular polyolefins.
In these metallocenes, the indenyl groups are joined by means of bivalent radicals which have two or more carbon atoms, such as -(CH2)2 groups or with atoms different from carbon.
These radicals are generally bound in different positions relating to the ring with five carbon atoms of both indenyl groups, as described in patent appli-cations EP-A-485,823, EP-A-372,414, WO 94/11406.
Metallocenes are also known, whose indenyl groups are joined by means of bivalent radicals bound in po-sition 4 of the ring with six carbon atoms of both in-denyl groups, as described in patent applications EP
693 502, WO 96/38458.
New metallocene compounds have now been found in which the bivalent radical is bound to the ring with five carbon atoms of a cyclopentadienyl, indenyl, fluorenyl group and to the ring with six carbon atoms of an indenyl group, which can be conveniently used as components of catalysts for the polymerization of ole-f ins .
An object of present invention relates, in par-ticular, to metallocene compounds having general for-mula ( I ) :
R,, t X.
R7 R3 NI~
X, R, RI
~I) wherein:
- R1 and R2 can independently occupy any of the free positions of the indene group;
- R1, R2, R3, R4, R5, R6, R-7 and R8 independently rep-resent hydrogen, halogen, preferably F, Cl or Br, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C->o hydrocarbyl group substituted with one or more halogen atoms, or a CI-C=o hydro-carbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, preferably Si, 0, N, S, P; in addition, any two, or both pairs, of the substituents R3, R4, R; and R5r adjacent to each other, are joined to each other to form a saturated or unsaturated C4-C20 cy-clic structure, said structure optionally contain-ing one or more of the heteroatoms specified above;
- M represents titanium, zirconium or hafnium; and - X1 and X2 each independently represent a group of an anionic nature bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
Typical examples of X1 and X2 are hydride, halide, preferably chloride, a linear or branched alkyl group, such as methyl, ethyl, butyl, isopropyl, isoamyl, oc-tyl decyl benzyl allyl, methyl-allyl, a cycloalkyl group such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, an aryl group, such as phenyl or toluyl, an alkoxyl or thioalkoxyl group, such as meth-oxyl, ethoxyl, iso- or sec-butoxyl, ethylsulfide, a carboxyl group, such as acetate, propionate, butyrate pivalate, versatate, naphthenate, or again, a dial-kylamide group, such as diethylamide, dibutylamide, or an alkylsilylamide group, such as bis(trimethylsilyl)amide.
X1 and X2 can also be chemically bound to each other and form a cycle having from 4 to 7 different hydrogen atoms, also comprising the metal M.
Typical examples of this aspect are divalent ani-onic groups such as the trimethylene or tetramethylene group, or the ethylenedioxy group.
The metallocene compounds of the present invention can exist in isomeric, racemic or meso forms.
A further object of the present invention relates to compounds having general formula (Ia) which are used for the preparation of the compounds having gen-eral formula ( I ) :
X1 and X2 can also be chemically bound to each other and form a cycle having from 4 to 7 different hydrogen atoms, also comprising the metal M.
Typical examples of this aspect are divalent ani-onic groups such as the trimethylene or tetramethylene group, or the ethylenedioxy group.
The metallocene compounds of the present invention can exist in isomeric, racemic or meso forms.
A further object of the present invention relates to compounds having general formula (Ia) which are used for the preparation of the compounds having gen-eral formula ( I ) :
R-, R3 R: Ri (1a) wherein:
- Rl, R2, R3, R4, R5, R6, R7 and R,3 have the meanings defined above.
Examples of structures of compounds having general formula (Ia), are indicated in Table 1 below:
- Rl, R2, R3, R4, R5, R6, R7 and R,3 have the meanings defined above.
Examples of structures of compounds having general formula (Ia), are indicated in Table 1 below:
Me M~ Mc75i ~ t {e9Si AIe \
S~fr.j bfe lvfe ~
l Me vte MqSi ~ Me Ph Ph Ph Ph 1de Ph Ph Table 1: Examples of structures of compounds with general formula (I) The compounds having general formula (Ia) can be prepared by means of a simple and original process which is illustrated in Scheme 1 below.
O Et 0 Et OH ~li td OH
a b -~ -r -~
R RI _ Ri RZ RI
d RS
R, R, R6 R9 r ~ H
Rg-3 f Rg ~---RZ Ri R Ri R Rt (Vin (vn c~) Scheme 1 a = LiBu(Zeq.)/hexane; b = diethylcarbonate; c =
PTSA/toluene; d = LiAlH4 or LiR or RMgX; e = PBr; f Li (C5HR3R9R5R6) In particular said process comprises the follow-ing steps:
(a) reaction of 1-indanol derivatives having formula (II), wherein the R1 and R2 groups have the meaning de-fined above, with LiBu to give the double salt having formula ( I I I ) ;
(b) reaction of the double lithium salt having for-mula (III), obtained in step (a), with electrophilic reagents, such as diethyl carbonate, to obtain hydroxy ester (IV);
(c) dehydration reaction of the alcohol function of the hydroxyester having formula (IV), obtained in step (b), carried out in an acid environment to give the ester (V) ;
(d) reduction reaction of the ester having formula (V), obtained in step (c), to obtain the alcohol (VI);
(e) bromination reaction of the alcohol having for-mula (VI) to give the bromine derivative (VII);
(f) formation reaction of the indenyl derivative hav-ing formula (Ia), starting from the bromine derivative having formula (VII) obtained in step (e) and from lithium salts of cyclopentadienyl anions, whose corre-sponding neutral derivative can be represented by the following general formula (VIII):
R;
R,4.
(vIIM
wherein each substituent R3, R4, R5 and R6 has the mean-ings defined above.
Step (a) of the process of the present invention is described in Chem. Ber. (1980) 113, 1304.
In particular, this article discloses that some benzyl alcohols and other phenyl carbinols, among which 1-indanol (Synthesis (1981) 59) can be deproto-nated in the presence of LiBu/tetramethylenediamine in pentane to give lithium(ortho-lithium)alkoxides.
The reaction described in step (a) can be carried out in the presence of base reagents such as, for ex-ample, lithium butyl, lithium methyl, sodium hydride in hydrocarbon and/or ether solvents or their mixtures at temperatures ranging from -30 to 120 C; the pre-ferred conditions comprise the use of lithium butyl in hexane at temperatures ranging from 0 to 70 C.
Typical 1-indanols having general formula (II) are 1-indanol, 2-methyl-l-indanol, 3-methyl-l-indanol, 3-ethyl-l-indanol, 4-methyl-l-indanol.
One of the advantages of the process of the pres-ent invention consists in the fact that many 1-indanol derivatives are available on the market or can be eas-ily prepared by means of well-known acyla-tion/alkylation reactions of aromatic rings suitably substituted.
Step (b) of the process of the present invention comprises the reaction of the double lithium salt, having general formula (III), with electrophilic rea-gents among which diethyl carbonate, dimethyl carbon-ate, carbon dioxide, ethyl chloroformiate, are par-ticularly appropriate for the purpose, in hydrocarbon and/or ether solvents or their mixtures at tempera-tures ranging from -100 to 120 C, preferably with di-ethyl carbonate in hexane at temperatures ranging from -70 to 25 C.
Step (c) of the process of the present invention consists in the dehydration of the hydroxy ester (IV) to obtain the corresponding indenyl derivative having general formula (V).
This reaction can be carried out in the presence of strong acids such as HC1, H2SO4, paratoluenesulfonic acid or blander dehydrating agents such as, for exam-ple, silica gel.
The choice of solvent for this reaction is very wide as it is possible to successfully use apolar sol-vents such as aliphatic hydrocarbons, medium polar solvents such as aromatic hydrocarbons or polar sol-vents such as ethers or chlorinated hydrocarbons; the temperature at which the reaction can take place can also be selected within a very wide range, typically from 25 to 150 C and the selection generally depends not only on the substrate, but also on the type of solvent used, preferably paratoluenesulfonic acid in toluene is used at temperatures ranging from 50 to 110 C.
Step (d) of the process of the present invention comprises the reduction of the ester group to alcohol with the formation of the compound having general for-mula (VI); this reduction can be carried out with various reagents among which LiAlH4, NaBH4, NaH, MgH2, LiBu, LiMe, MeMgCl, PhMgBr, ButMgCl, generally in ether solvents, but it is also possible to use alternative solvents having other characteristics, at temperatures ranging from -70 to 100 C; LiAl4 in ethyl ether is preferably used at temperatures ranging from -30 to 25 C.
Step (e) of the process of the present invention comprises the bromination of the alcohol function to give the bromine derivative having general formula (VII); also in this case there are various synthetic alternatives, well known to experts in the field, which comprise the use of various brominating agents in different solvents; the preferred conditions com-prise the use of PBr3 in methylene chloride at tempera-tures ranging from -20 to 25 C.
Step (f) of the process of the present invention, comprises the reaction of a cyclopentadienyl anion with the bromine derivative having general formula (VII), obtained by the reaction of the corresponding neutral derivative, having general formula (VIII), with a suitable base.
Experts in the field know that there is a wide variety of products capable of satisfying this re-quirement; it is in fact possible to use alkyls or hy-drides of electro-positive metals such as, for exam-ple, lithium methyl, lithium butyl, lithium ter-butyl, magnesium dibutyl, sodium hydride, potassium hydride, magnesium hydride, the well-known Grignard reagents:
RMgX, or also the alkaline or earth-alkaline metals themselves or their alloys.
All the reagents are generally easy to find on the market, with acceptable costs, and consequently their selection frequently depends on the type of sub-strate whose anion is to be obtained.
The solvents for effecting this reaction can be selected from aliphatic or aromatic hydrocarbons, ethers and/or their mixtures, the preference of one or the other often depending on the particular demands of solubility or reaction rate of the case in question.
The temperatures at which the reaction is carried out can vary within a very wide range, typically from -80 to 110 C and essentially depend on the thermal stability of the substrates and on the solvent used.
The preferred conditions for obtaining the anions of the compound having general formula (VIII) comprise the use of lithium butyl in mixtures of hexane/THF at temperatures ranging from 00 to 60 C.
Typical compounds having general formula (VIII) are: cyclopentadiene, methyl-cyclopentadiene, tetrame-thyl-cyclopentadiene, trimethylsilyl-cyclopentadiene, indene, 3-meth-yl-indene, 4,7-dimethyl-indene, 5,6-dimethyl-indene, 4,5,6,7-tetrahydro-indene, 4,5,6,7-tetrahydro-2-methyl-ind-ene, 2,4,5,6,7,8-hexahydro-azulene, 2-methyl-2,4,5,6,7,8-hexahydro-azulene, 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyc-lo-octene, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopen-tacyclododecene, fluorene, 1,2,3,4,5,6,7,8-octa-hydro-fluo-rene.
In the preferred embodiment, the compound having general formula (VIII) is cyclopentadiene, tetrame-thyl-cyclopentadiene, indene, 3-methyl-indene, 4,7-dimethyl-indene, 2,4,5,6,7,8-hexahydro-azulene, fluo-rene.
In an even more preferred embodiment the compound having general formula (VIII) is indene, 4,7-dimethyl-indene.
This reaction can be carried out in a wide vari-ety of solvents selected from aromatic and/or ali-phatic hydrocarbons and from ethers and/or their mix-tures, at a temperature ranging from -80 to 120 C.
There are no particular limitations in the order of addition of the various reagents, but it is preferable to operate by adding the bromine derivative (VII), ei-ther pure or diluted in ether solvent, to the solu-tion/suspension containing the cyclopentadienyl anion, obtained as described above, at temperatures ranging from -70 to 25 C.
Alternatively, step (f) of the process of the present invention can be carried out by reacting the brominated product (VII) with a suitable lithium eno-late giving rise to the formation of indenyl-cyclopentadienyl products having general formula (XIII) :
R!
Rg R, R
RIo Ri i GXIIn wherein:
- R1 and R2 can independently occupy any of the free positions of the indene group;
- Rl, R2, R7, R8, R9, Rio and Rll independently repre-sent hydrogen, halogen, preferably F, Cl or Br, a linear or branched C1-C2o hydrocarbyl group, satu-rated or unsaturated, cycloaliphatic or aromatic, or a C1-C2o hydrocarbyl group substituted with one or more halogen atoms, or a C1-C2o hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, pref-erably Si, 0, N, S, P, or, wherein any two of the substituents R9r Rlo and Rll, adjacent to each other, are joined to each other to form a satu-rated or unsaturated C4-C20 cyclic structure, com-prising a bond of the cyclopentadienyl ring, said structure optionally containing one or more of the heteroatoms specified above;
- R12 can be independently hydrogen, a linear or branched C1-C20 hydrocarbyl group, saturated or un-saturated, cycloaliphatic or aromatic, or a C1-C20 hydrocarbyl group comprising one or more heteroa-toms of groups 14 to 16 of the periodic table of elements, preferably Si, 0, N, S, P.
The variant in step (f) of the process of the present invention is indicated in Scheme 2:
9 Li Li O
Rto Rto Rto Ri t Rti Rt t (IX) (Xa) (Xb) h Ri Ri Rt R7 R~ R~
Rs R2 Rs R2 Rs RZ
Rg Rtz 41 OH
Rto Rto R12 Rto Rt t Ri i Rt i CA= (XII) (X) 15 Scheme 2 g:Li[N(iso-Pr)2/THF/-78 C,h:(VII)/THF;i:NaBH4 or LiR12 or R,2MgX;1:CuSO4/ toluene/110 C.
In accordance with this, a further object of the present invention relates to a variant of the process 20 for the preparation of compounds having general for-mula (Ia), which gives rise to the formation of analo-gous products having general formula (XIII) wherein the substituents R1, Rzr R7, R8, Rg, Rlo, Rll and R12 have the meaning defined above, which comprises the follow-25 ing steps:
(g) reaction of a cyclic ketone, having general for-mula (IX), wherein the groups R9r Rlo and R11 have the meaning defined above, with a lithium amide to give the mixture of anions having general formula (Xa) / (Xb) ;
(h) reaction of the mixture of anions (Xa)/(Xb) with the brominated product having general formula (VII), prepared according to what is indicated above (Scheme 1) ;
(i) reduction of the functional carbonyl group to al-cohol, by means of suitable reagents, with the forma-tion of the derivative having general formula (XII), wherein the R12 group has the meaning defined above;
(1) dehydration of the derivative having general for-mula (XII), obtained in step (i), with the formation of the desired indenyl-cyclopentadienyl compound, hav-ing general formula (XIII), wherein the groups R1r R2, R7, Rer R9, Rlo, Rll and R12 have the meaning defined above.
In step (g) a cyclic ketone having general for-mula (IX) is reacted with a strong non-alkylating base, in ether solvents such as ethyl ether, tetrahy-drofuran, dioxane, as the dissolving capacity of the latter can improve the reaction kinetics, but this does not mean that less polar solvents, such as aro-matic and/or aliphatic hydrocarbons, can also be con-veniently used for the purpose, at temperatures rang-ing from -80 C to 110 C, the selection of the latter depending on the type of solvent and substrates used.
Typical strong bases, suitable for the purpose, are alcoholates of alkaline and earth-alkaline metals such as for example lithium methoxide, sodium methox-ide, sodium ethoxide, sodium iso-propoxide, potassium ter-butoxide, magnesium di-ethoxide, etc. or the rela-tive amides such as, for example, lithium amide, so-dium amide, lithium di-ethylamide, lithium di-isopropylamide, lithium bis-(trimethylsilyl)amide, po-tassium di-butylamide, etc.
In the preferred embodiment the strong bases are selected from lithium methoxide, sodium ethoxide, po-tassium ter-butoxide, sodium amide, lithium di-isopropylamide.
In an even more preferred embodiment the strong base is lithium di-isopropylamide.
Typical cyclic ketones having general formula (IX), suitable for being used in step (g) of Scheme 2 are: cyclopent-l-en-3-one, 1-methyl-cyclopent-l-en-3-one, 1,2,5-tri-methyl-cyclopent-l-en-3-one, indan-l-one, 3-methyl-indan-l-one, 4,7-dimethyl-indan-l-one, indan-2-one, etc.
In the preferred embodiment the cyclo-ketone com-pound having general formula (IX) is selected from cy-clopent-l-en-3-one, 1,2,5-trimethylcyclopent-l-en-3-one, indan-l-one, 3-methyl-indan-l-one; in an even more preferred embodiment compound (IX) is indan-l-one.
Step (h) of the process of the present invention consists in the reaction between the mixture of anions (Xa)/(Xb) with the brominated product (VII), prepared according to Scheme 1, which can be carried out in hy-drocarbon, ether solvents or their mixtures, the use of the same solvent adopted in the previous step (g), at temperatures ranging from -80 C to 70 C, normally being preferred.
In a preferred embodiment, the reaction is car-ried out in a mixture of THF/hexane at temperatures ranging from -70 to 25 C.
Step (i) of the process of the present invention consists in a reduction of the functional carbonyl group, present in the derivative having general for-mula (XI), to alcohol, with the formation of the com-pound having general formula (XII). There are various possibilities, well known to experts in the field, for selecting the reducing reagents suitable for the pur-pose, among which lithium aluminum hydride, sodium bo-ron hydride, sodium hydride, lithium methyl, lithium phenyl, ethyl magnesium bromide, isopropyl magnesium bromide, etc., which can be successfully used either in hydrocarbon or ether solvents or their mixtures, at temperatures ranging from -40 to 70 C. In a preferred embodiment, sodium boron hydride in tetrahydrofuran is used at temperatures ranging from -20 to 25 C.
Step (1) of the process of the present invention, consists in the dehydration of the derivative (XII), obtained in step (i), to give the desired indenyl-cyclopentadienyl product having general formula (XI I I ) .
The latter can be carried out in the presence of dehydrating agents such as, for example, silica gel, strong acids such as HC1, H2SO9, paratoluenesulfonic acid, or anhydrous inorganic salts such as, for exam-ple, Cu ( S04 ), Mg ( S09 ), Na (S04) 2, CaC12, etc.
The selection of the solvent for this reaction is very wide as it is possible to successfully use apolar solvents such as aliphatic hydrocarbons, medium polar solvents such as aromatic hydrocarbons or polar sol-vents such as ethers or chlorinated hydrocarbons; the temperature at which the reaction takes place can also be selected within a very wide range, typically from -20 to 130 C and the selection generally depends not only on the substrate but also on the type of solvent used. In a preferred embodiment anhydrous Cu(S09) is used in toluene at 110 C.
The processes of the present invention do not necessarily require the isolation of the single reac-tion products at the end of the respective steps.
In addition to the advantage of starting from products which are easily available, the processes comprise quite simple chemical passages and produce satisfactory overall yields.
The preparation of the complexes having general formula (I) can be carried out according to one of the well-known methods described in literature for the production of bridged bis-cyclopentadienyl complexes of transition metals.
The method most commonly used comprises reacting a salt of the metal M (preferably a chloride), with a salt of an alkaline metal of the dianion of the bis-cyclo-pentadienyl ligand having the desired structure.
The preparation of the complexes having formula (I) normally comprises two steps, in the first of which the ligand having general formula (Ia) is re-acted with a lithium alkyl, such as lithium methyl or lithium butyl, in an inert solvent, preferably con-sisting of an aromatic hydrocarbon or an ether, par-ticularly tetrahydrofuran or ethyl ether.
The temperature during the reaction is preferably maintained below room temperature to avoid the crea-tion of secondary reactions. At the end of the reac-tion the corresponding lithium salt of the cyclopenta-dienyl dianion is obtained.
In the second step, the salt of the cyclopentadi-enyl dianion is reacted with a salt, preferably a chloride, of the transition metal M, again in an inert organic solvent at a temperature preferably ranging from -30 to 70 C.
At the end of the reaction, the complex having formula (I) thus obtained is separated and purified according to the known methods of organometallic chem-istry.
As is known to experts in the field, the above operations are sensitive to the presence of air and humidity and should therefore be carried out in an in-ert atmosphere, preferably under nitrogen or argon.
Numerous general and specific methods which sub-stantially originate from the method indicated above, are described in literature, such as, for example in the publications of D.J. Cardin "Chemistry of Organo Zr and Hf Compounds" J. Wiley and Sons Ed., New York (1986); R. Haltermann "Chemical Review", vol. 92 (1992) pages 965-994; R.O. Duthaler and A. Hafner "Chemical Review", vol. 92 (1992) pages 807-832.
The metallocene compounds of the present inven-tion can be conveniently used as catalytic components for the polymerization of olefins.
A further object of the present invention there-fore relates to a catalyst for the polymerization of olefins comprising the reaction product between:
(A) a metallocene compound having formula (I) ob-tained as described above, and (B) one or more compounds capable of activating the metallocene (I) selected from those known in the art, particularly an organic derivative of an element M' different from carbon and selected from the elements of groups 1, 2, 12, 13 and 14 of the periodic table.
In particular, according to the present inven-tion, said element M' is selected from boron, alumi-num, zinc, magnesium, gallium and tin, more particu-larly boron and aluminum.
In a preferred embodiment of the present inven-tion, the component (B) is an organo-oxygenated de-rivative of aluminum, gallium or tin. This can be de-fined as an organic compound of M' , in which the lat-ter is bound to at least one oxygen atom and to at least one organic group consisting of an alkyl group having from 1 to 12 carbon atoms, preferably methyl.
According to this aspect of the invention, compo-nent (B) is more preferably an aluminoxane. -As is known, aluminoxanes are compounds containing Al-O-Al bonds, with a varying O/Al ratio, which can be ob-tained, under controlled conditions, by the reaction of an aluminum alkyl or aluminum alkyl halide, with water or other compounds containing pre-established quantities of water available, such as, for example, in the case of the reaction of aluminum trimethyl with aluminum sulfate hexahydrate, copper sulfate pentahy-drate or iron sulfate pentahydrate.
Aluminoxanes preferably used for the formation of the polymerization catalyst of the present invention are oligo- poly-meric, cyclic and/or linear compounds, characterized by the presence of repetitive units hav-ing the following formula:
wherein R13 is a C1-C12 alkyl group, preferably methyl.
Each dialuminoxane molecule preferably contains from 4 to 70 repetitive units which may also not all be equal to each other, but contain different R13 groups.
When used for the formation of a polymerization catalyst according to the present invention, the alu-minoxanes are put in contact with a complex having formula (I) in such proportions that the atomic ratio between Al and the transition metal M is within the range of 10 to 10000 and preferably from 100 to 5000.
The sequence with which the complex (I) and the alu-minoxane are put in contact with each other, is not particularly critical.
In addition to the above aluminoxanes, the defi-nition of component (B) according to the present in-vention also comprises galloxanes (in which, in the previous formulae, gallium is present instead of alu-minum) and stannoxanes, whose use as cocatalysts for the polymerization of olefins in the presence of met-allocene complexes is known, for example, from patents US 5,128,295 and US 5,258,475.
According to another preferred aspect of the pre-sent invention, said catalyst can be obtained by put-ting component (A) consisting of at least on complex having formula (I), in contact with component (B) con-sisting of at least one compound or a mixture of or-ganometallic compounds of M' capable of reacting with the complex having formula (I), extracting from this a 6-bound group R' to form, on the one hand at least one neutral compound, and on the other hand an ionic com-pound consisting of a metallocene cation containing the metal M and an organic non-coordinating anion con-taining the metal M', whose negative charge is delo-calized on a multicenter structure.
Components (B) suitable as ionizing systems of the above type are preferably selected from the volu-minous organic compounds of boron and aluminum, such as for example, those represented by the following general formulae:
[ (Rc) xNH4-x] + [B (RD) 4 ] : B (RD) 3 : [Ph3C] + [B (RD) 4 ] i [(Rc)3PH]+[B(RD)4] : [Li]+[B(RD)4] : [Li]+[Al(RD)4] ;
wherein the deponent "x" is an integer ranging from 0 to 3, each Rc group independently represents an alkyl or aryl radical having from 1 to 12 carbon atoms and each RD group independently represents an aryl radical partially or, preferably, totally fluorinated, having from 6 to 20 carbon atoms.
Said compounds are generally used in such quanti-ties that the ratio between the atom M' of component (B) and the atom M of component (A) is within the range of 0.1 to 15, preferably from 0.5 to 10, more preferably from 1 to 6.
Component (B) can consist of a single compound, normally an ionic compound, or a combination of this compound with MAO, or, preferably, with an aluminum trialkyl having from 1 to 16 carbon atoms in each al-kyl residue, such as for example A1Me3, AlEt3, A1(i-Bu)3.
In general, the formation of the ionic metallo-cene catalyst, in accordance with the present inven-tion, is preferably carried out in an inert liquid me-dium, more preferably hydrocarbon. The selection of components (A) and (B) which are preferably combined with each other, as well as the particular method used, can vary depending on the molecular structures and result desired, according to what is described in detail in specific literature available to experts in the field.
Examples of these methods are qualitatively sche-matized in the list provided hereunder, which however does not limit the overall scope of the present inven-tion:
(i) by contact of a metallocene having general for-mula (I) wherein at least one, preferably both, of the substituents X1 and X2 is hydrogen or an alkyl radical, with an ionic compound whose ca-tion is capable of reacting with one of the substituents X1 or X2 to form a neutral com-pound, and whose anion is voluminous, non-coordinating and capable of delocalizing the negative charge;
(ii) by the reaction of a metallocene having the previous formula (I) with an alkylating agent, preferably an aluminum trialkyl, used in molar excess of 10/1 to 500/1, followed by the reac-tion of a strong Lewis acid, such as for exam-ple, tris(pentafluo-rophenyl)boron a in more or less stoichiometric quantity or in slight ex-cess with respect to the metal M;
(iii) by contact and reaction of a metallocene having the previous formula (I) with a molar excess of 10/1 to 1000/1, preferably from 30/1 to 500/1 of an aluminum trialkyl or an alkylaluminum halide or one of their mixtures, which can be represented by the formula AlR,,X3-,n, wherein R
is a linear or branched C1-C1Z alkyl group, X is a halogen, preferably chlorine or bromine, and "m" is a decimal number ranging from 1 to 3;
followed by the addition to the composition thus obtained, of at least an ionic compound of the type described above in such quantities that the ratio between B or Al and the atom M
in the metallocene complex is within the range of 0.1 to 20, preferably from 1 to 6.
Examples of ionizing ionic compounds or multicomponent reactive systems capable of producing an ionic cata-lytic system by reaction with a metallocene complex, according to the present invention, are described in the following patent publications, whose content in herein incorporated as reference:
= European patent application, published under the Nr.: EP-A 277,003, EP-A 277,004, EP-A 522,581, EP-A 495,375, EP-A 520,732, EP-A 478,913, EP-A
468,651, EP-A 427,697, EP-A 421,659, EP-A
418,044;
= International patent applications published under the Nr.: WO 92/00333, WO 92/05208; WO 91/09882;
= Patents U.S. 5,064,802, U.S. 2,827,446, U.S.
5, 066, 739.
Also included in the scope of the present inven-tion are those catalysts comprising two or more com-plexes having formula (I) mixed with each other. Cata-lysts of the present invention based on mixtures of complexes having different catalytic activities can be advantageously used in polymerization when a wider mo-lecular weight distribution of the polyolefins thus produced is desired.
According to an aspect of the present invention, in order to produce solid components for the formation of catalysts for the polymerization of olefins, the above complexes can also be supported on inert solids, preferably consisting of oxides of Si and/or Al, such as for example, silica, alumina or silica-aluminates.
For the supporting of said catalysts, the known supporting techniques can be used, normally comprising contact, in a suitable inert liquid medium, between the carrier, optionally activated by heating to tem-peratures exceeding 200 C, and one or both of compo-nents (A) and (B) of the catalyst of the present in-vention. For the purposes of the present invention, it is not necessary for both components to be supported, as it is also possible for only the complex having formula (I) or the organic compound of B, Al, Ga or Sn as defined above, to be present on the surface of the carrier. In the latter case, the component which is not present on the surface is subsequently put in con-tact with the supported component, at the moment of the formation of the catalyst active for the polymeri-zation.
Also included in the scope of the present inven-tion are the complexes, and catalytic systems based on these, which have been supported on a solid by means of the functionalization of the latter and formation of a covalent bond between the solid and a metallocene complex included in formula (I) above.
A particular method for the formation of a sup-ported catalyst according to the present invention comprises pre-polymerizing a relatively small fraction of monomer or mixture of monomers in the presence of the catalyst, so as to include this in a solid micro-particulate, which is then fed to the actual reactor itself for completing the process in the presence of an additional olefin(s). This provides a better con-trol of the morphology and dimensions of the polymeric particulate obtained at the end.
One or more other additives or components can be optionally added to the catalyst according to the pre-sent invention, as well as the two components (A) and (B), to obtain a catalytic system suitable for satis-fying specific requisites. The catalytic systems thus obtained should be considered as being included in the scope of the present invention. Additives or compo-nents which can be included in the preparation and/or formulation of the catalyst of the present invention are inert solvents such as, for example, aliphatic and/or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly co-ordinating additives (Lewis bases) selected, for example, from non-polymerizable olefins, ethers, tertiary amines and alcohols, halogenating agents such as silicon halides, halogenated hydrocar-bons, preferably chlorinated, and the like, and again all other possible components normally used in the art for the preparation of the traditional homogeneous catalysts of the metallocene type for the (co)polymerization of olefins.
Components (A) and (B) form the catalyst of the present invention by contact with each other, prefera-bly at temperatures ranging from 200 to 60 C and for times varying from 10 seconds to 1 hour, more prefera-bly from 30 seconds to 15 minutes.
The catalysts according to the present invention can be used with excellent results in substantially all known (co)polymerization processes of olefins, ei-ther in continuous or batchwise, in one or more steps, such as, for example, processes at low (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa) pressure, at temperatures ranging from 10 to 240 C, optionally in the presence of an inert diluent. Hydrogen can be con-veniently used as molecular weight regulator.
These processes can be carried out in solution or suspension in a liquid diluent normally consisting of an aliphatic or cycloaliphatic saturated hydrocarbon, having from 3 to 20 carbon atoms or a mixture of two or more of these, but which can also consist of a monomer as, for example, in the known co-32 ' polymerization process of ethylene and propylene in liquid propylene. The quantity of catalyst introduced into the polymerization mixture is preferably selected so that the concentration of the metal M ranges from 10-9 to 10-$ moles/liter.
Alternatively, the polymerization can be carried out in gas phase, for example, in a fluid bed reactor, normally at pressures ranging from 0.5 to 5 MPa and at temperatures ranging from 50 to 150 C.
According to a particular aspect of the present invention, the catalyst for the (co) polymerization of ethylene with other olefins is prepared separately (preformed) by contact of components (A) and (B), and is subsequently introduced into the polymerization en-vironment.
The catalyst can be first charged into the polym-erization reactor, followed by the reagent mixture containing the olefin or mixture of olefins to be po-lymerized, or the catalyst can be charged into the re-actor already containing the reagent mixture, or fi-nally, the reagent mixture and the catalyst can be contemporaneously fed into the reactor.
According to another aspect of the present inven-tion, the catalyst is formed "in situ", for example by introducing components (A) and (B) separately into the polymerization reactor containing the pre-selected olefinic monomers.
The catalysts according to the present invention can be used with excellent results in the polymeriza-tion of ethylene to give linear polyethylene and in the copolymerization of ethylene with propylene or higher olefins, preferably having from 4 to 12 carbon atoms, to give copolymers having different charaCter-istics depending on the specific polymerization condi-tions and on the quantity and structure of the comono-mer used.
For example, linear polyethylenes can be ob-tained, with a density ranging from 0.880 to 0.940, and with molecular weights ranging from 10,000 to 2,000,000. The olefins preferably used as comonomers of ethylene in the production of low or medium density linear polyethylene (known with the abbreviations ULDPE, VLDPE and LLDPE depending on the density), are 1-butene, 1-hexene and 1-octene.
The catalyst of the present invention can also be conveniently used in copolymerization processes of ethylene and propylene to give saturated elastomeric copolymers vulcanizable by means of peroxides and ex-tremely resistant to aging and degradation, or in the terpolymerization of ethylene, propylene and a diene, generally non-conjugated, having from 4 to 20 carbon atoms, to obtain vulcanizable rubbers of the EPDM
type.
In the case of these latter processes, it has been found that the catalysts of the present invention allow the production of polymers having a particularly high comonomer content and average molecular weight under the polymerization conditions.
In the case of the preparation of EPDM, the di-enes which can be used for the purpose are preferably selected from:
= linear chain dienes such as 1,4-hexadiene and 1,6-octadiene;
= branched dienes such as 5-methyl-l,4-hexadiene;
3,7-dimethyl-l,6-octadiene; 3,7-dimethyl-1,7-octadiene;
= dienes with a single ring such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene; 1,5-cyclododecadiene;
= dienes having bridged condensed rings such as di-cyclopentadiene; bicyclo[2.2.1]hepta-2,5-diene;
alchenyl, alkylidene, cycloalkenyl and cycloalky-lidene norbornenes such as 5-methylene-2-norbornene, 5-ethylidene-2-borbornene (ENB), 5-propenyl-2-norbornene.
Among the non-conjugated dienes typically used for preparing these copolymers, dienes containing at least one double bond in a stretched ring are pre-ferred, even more preferably 5-ethylidene-2-norbornene (ENB), and also 1,4-hexadiene and 1,6-octadiene.
In the case of EPDM terpolymers, it is convenient for the quantity of dienic monomer not to exceed 15%
by weight, and it is preferably from 2 to 10% by weight. The propylene content on the other hand ranges from 20 to 55% by weight.
The catalysts of the present invention can also be used in homo- and co-polymerization processes of olefins according to the known techniques, giving, with excellent yields, atactic, isotactic or syndio-tactic polymers, depending on the structure and geome-try of the metallocene complex having formula (I).
Olefins suitable for the purpose are those having from 3 to 20 carbon atoms, optionally also comprising halogens and/or other heteroatoms or aromatic nuclei such as, for example, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-l-pentene, 1-decene and styrene.
The present invention is further described by the following examples, which, however, are provided for purely illustrative purposes and do not limit the overall scope of the invention itself.
CHARACTERIZATION METHODS
The analytical techniques and characterization methods used in the examples are listed below and are briefly described.
The characterization by means of NMR spectroscopy mentioned in the following examples was carried out on a nuclear magnetic resonance spectrometer mod. Bruker MSL-300, using, unless otherwise specified, CDC13 as solvent for each sample.
The molecular weight measurement of the olefinic polymers was carried out by means of Gel-Permeation Chromatography (GPC). The analyses of the samples were effected in 1,2,4-trichlorobenzene (stabilized with Santonox) at 135 C with a WATERS 150-CV chromatograph using a Waters differential refractometer as detector.
The chromatographic separation was obtained with a set of -Styragel HT columns (Waters) of which three with pore dimensions of 103, 109, 105 A respectively, and two with pore dimensions of 106 A, establishing a flow-rate of the eluant of 1 ml/min. The data were obtained and processed by means of Maxima 820 software version 3.30 (Millipore); the number (Mõ) and weight (Mw) aver-age molecular weight calculation was carried out by universal calibration, selecting polystyrene standards with molecular weights within the range of 6,500,000-2,000, for the calibration.
The determination of the content of units deriv-ing from propylene and possible diene in the polymers is carried out (according to the method of the Appli-cant) by means of IR on the same polymers in the form of films having a thickness of 0.2 mm, using an FTIR
Perkin-Elmer spectrophotometer model 1760. The inten-sity of the characteristic peaks is measured, of pro-pylene at 4390 cm 1 and ENB at 1688 ciri 1 respectively, in relation to the peak at 4255 cm"1, and the quantity is determined using a standard calibration curve.
The Melt Flow Index (MFI) of the polymers is de-termined in accordance with the regulation ASTM D-1238 D.
The Mooney viscosity (1+4) is determined at 100 C
using a Monsanto "1500 S" viscometer according to the method ASTM D 1646/68.
Synthesis of 1-methyl-4-methylene(1-indenyl)indene The following products are reacted:
170 ml of benzene 22.7 g (264 mmoles) of crotonic acid 106 g (795.2 mmoles) of aluminum trichloride o + ~ -~
The solution of crotonic acid in 100 ml of ben-zene is added dropwise to the suspension of A1C13 in 70 ml of benzene. The mixture is stirred at 80 C for 5 hours. It is poured into ice and is extracted with ethyl ether. After washing until neutrality with a saturated aqueous solution of NaHCO3 and water and an-hydrifying on Na2SO4, the solvent is evaporated. The product is purified by distillation (Tboil. = 125 C) 32.0 g are obtained (yield = 830).
32.0 g (219.2 mmoles) of 3-methyl-l-indanone, ob-tained in the previous step, are reacted with:
5.6 g (147 mmoles) of sodium boronhydride 128 ml of tetrahydrofuran 64 ml of methanol O OH
NaBH4 o -~
NaBH4 is added, in portions, to the solution of 3-methyl-l-indanone in tetrahydrofuran and methanol, at 0 C. After 2 hours the mixture is poured into ice and is extracted with ethyl ether. After washing the or-ganic extracts to neutrality with a saturated solution of NaCl and anhydrifying on Na2SO4, the mixture is fil-tered and the solvent evaporated. 30.8 g of product are obtained (95%).
14.8 g (0.1 moles) of 3-methyl-l-indanol, ob-tained in the previous step, are reacted with:
80 ml (0.2 moles) of LiBu 2.5 M in hexane 26.7 ml (0.22 moles) of diethylcarbonate 500 ml of hexane OH COOEt OH
1) LiBu 2) ~o N-butyl lithium is added, by means of a drip fun-nel, over a period of about 1 h, in an inert atmos-phere, to the suspension of 3-methyl-l-indanol in hex-ane, at 20 C. At the end of the addition the reaction mixture is heated to 60 C for 2 h, and, after cooling to -70 C, diethyl carbonate is then added. The tem-perature is left to rise slowly to 25 C and, after a further 8 h, the reaction mass is poured into water and is extracted with ethyl ether. The separated or-ganic phase is washed with water until neutrality, an-hydrified on sodium sulfate and the solvent is evapo-rated at reduced pressure. After purification on a silica gel column (eluant: hexane/ethyl acetate 9/1), 5.6 g of 3-methyl-7-carboethoxy-l-indanol are ob-tained.
5.6 g (25.45 mmoles) of 3-methyl-7-carboethoxy-l-indanol 80 ml of toluene 0.1 g (0.58 mmoles) of p-toluenesulfonic acid (PTSA) COOEt OH COOEt PTSA
Para-toluenesulfonic acid is added to the solu-tion of 3-methyl-7-carboethoxy-l-indanol in toluene.
The mixture is heated to 100 C and the water is re-moved by azeotropic distillation. After 2 h a satu-rated aqueous solution of NaHCO3 is added, the organic phase is separated, washed with water until neutrality and anhydrified on NaSO4. Finally the solvent is re-moved at reduced pressure and, after purification on a silica gel column (eluant: hexane/ethyl acetate 95/5), 5.0 g of 3-methyl-7-carboethoxy-l-indene are obtained.
5.0 g (24.7 mmoles) of 3-methyl-7-carboethoxy-l-indene 0.6 g (15. 8 mmoles ) of LiAlH4 100 ml of ethyl ether OH
COOEt L'A~a O Et20 O
A solution of 3-methyl-7-carboethoxy-l-indene in 40 ml of ethyl ether are added, at -30 C, to the sus-pension of LiAlHg in 60 ml of ethyl ether. The tempera-ture is slowly left to rise to 25 C and after 30 min water is slowly added and the mixture is acidified with HC1 2M. The reaction mass is extracted with ethyl ether, washed repeatedly with water until neutrality and dried on NaSO9. The solvent is finally removed un-der vacuum and 3.76 g of 7-(3-methylindenyl) methanol are obtained.
3.76 g (23.5 mmoles) of 7-(3-methylindenyl)methanol 2.1 g (7.86 mmoles) of PBr3 50 ml of methylene chloride OH Br O PBT3 0 ~
CH,C12 Phosphorous tribromide is slowly added, by means of a drip funnel, to the solution of 7-(3-methylindenyl) methanol in CH2C12, cooled to -20 C. The temperature is left to rise to 25 C and after 30 min a saturated aqueous solution of NaHCO3 is slowly added.
The reaction mass is extracted various times with ethyl ether, the organic extracts are washed with wa-ter until neutrality and dried on NaS09. After removing the solvent at reduced pressure, 4.9 g of 4-bromomethyl-l-methylindene are obtained.
7 g (31.4 mmoles) of 4-bromomethyl-l-methylindene, ob-tained in the previous step, are reacted with:
31 ml (77.5 mmoles) of LiBu 2.5 M in hexane 200 ml of THF
7.3 ml (62.3 mmoles) of indene CH2Br BuLi 00 co Li++ Ct11- CH2 Butyl lithium is added dropwise to the solution of indene in 100 ml of THF. The mixture is left under stirring for 2h at room temperature and is then cooled to -70 C. Bromine dissolved in THF is added. After 1 h at this temperature the mixture is left to rise to room temperature and is poured into water. It is ex-tracted with ethyl ether, the extracts are washed un-til neutrality and are anhydrified on sodium sulfate.
The residue obtained by evaporation of the solvent is purified on a silica gel column using petroleum ether as eluant. In this way 4.3 g of 1-methyl-4-methylene (1-indenyl)indene are obtained (53% yield).
Synthesis of 4-methylene(1-indenyl)indene The following products are reacted:
16.0 g (119.4 mmoles) of 1-indanol 100 ml (250 mmoles) of LiBu 2.5 M in hexane 31.5 (259.6 mmoles) of diethylcarbonate 500 ml of hexane OEt O
H LiBu w ~
^o ~o ^
N-butyl-lithium is added dropwise to the suspen-sion in 1-indanol in hexane, at -5 C. The mixture is stirred at 60 C for 2 hours and diethylcarbonate is added, at -70 C. The mixture is left to rise to room temperature. After 8 hours, it is poured into water and extracted with ethyl ether. After washing the or-ganic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated under vacuum. The product is purified by chromatographic separation on silica gel eluating with hexane and ethyl acetate in a ratio of 95/5. 6 g of product are obtained (yield=24.50).
g (24.3 mmoles) of hydroxy-ester, obtained in the previous step, are reacted with:
200 mg (1.05 mmoles) of para-toluenesulfonic acid 20 ml of toluene 5 EtO OEt0 H
O PTSA
--~ o The toluene solution of hydroxy ester and PTSA
are stirred at 90 C for 3 hours. The mixture is washed, until neutrality, with a saturated aqueous so-lution of NaHCO3 and with water. After anhydrifying the organic phase on Na2SO4 and filtering, the solvent is evaporated. The residue is purified on a silica gel chromatographic column with hexane and ethyl acetate as eluant in a ratio of 95/5. 4.0 g of ester are thus obtained (yield 87.7%).
8.8 g (46.8 mmoles) of ester, obtained in the previous step, are reacted with:
2.1 g (55.3 mmoles) of lithium aluminum hydride 120 ml of ethyl ether.
OEt O H
The ester dissolved in 20 ml of ethyl ether is added, at -20 C to the suspension, in ethyl ether, of LiAlH4. After 6 hours water is slowly added, the mix-ture is acidified with HC1 (2N) and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the mixture is filtered and the solvent evaporated. 6.6 g of alcohol are obtained (yield 96%).
6.6 g (45.2 mmoles) of alcohol, obtained in the previous step, are reacted with:
1.5 ml (15.82 mmoles) of phosphorous tribromide 70 ml of methylene chloride H Br \ PBr3 \
O --~ O
The phosphorous tribromide is added dropwise to the solution, in methylene chloride, of alcohol at -20 C. After 1 hour a saturated aqueous solution of NaHCO3 is added dropwise and the mixture is extracted several times with ethyl ether. After washing the or-ganic extracts to neutrality and anhydrifying on Na2SO4, the mixture is filtered and the solvent evapo-rated. 5.0 g of 4-bromomethyl-indene are obtained (yield 530) .
4.44 ml (33.6 mmoles) of inderie 15 ml (33.6 mmoles) of LiBu solution 2.5 M in hexane g (24 mmoles) of 4-bromomethyl-indene 90 ml of tetrahydrofuran 5 45 ml of hexane nBuLi DoU4 Br Indenyl-lithium o -~
N-butyl-lithium is added, at 5 C, to the solu-tion, in THF in hexane, of indene. After 1 hour, the mixture is cooled to -70 C and benzyl bromide dis-solved in 20 ml of THF is added. The mixture is left to rise to room temperature. After 8 hours, it is poured into water and is extracted with ethyl ether.
After washing the ether extracts to neutrality with water and anhydrifying on Na2SO4, the mixture is fil-tered and the solvent evaporated.
After purification on a silica gel chroma-tographic column (eluant: hexane), 2.3 g of 4-methylene(1-indenyl) indene are obtained (yield 39.3%) EXP,MPLE 3 Synthesis of 7-methyl-4-methylene(4,7-dimethyl-l-indenyl)-indene The following reaction scheme is followed:
OOEt COOEt EtONa/EtOH &--( + <OOEt Et OOEt ])KOH cJ_*_./cOOW. ~ ~Et 2)H+
~11OOH SOC12 ~OC1 A1C13 ~ 0 2 0 oci -Q\
108.0 g (583.7 mmoles) of o-methylbenzylbromide 150 ml (988 mmoles) of dimethylmalonate 21.4 g (930 mmoles) of sodium 350 ml of ethyl alcohol 25 g (445 mmoles) of KOH
30 ml of thionyl chloride 38 g (285.7 mmoles) of aluminum trichloride Metal sodium is added, in portions, to the etha-nol. Diethylmalonate is slowly added dropwise to the solution of sodium ethylate in ethanol, at 50 C, and then o-methyl-benzylbromide is added rapidly. The mix-ture is kept under stirring at boiling point for 2 hours. After evaporating most of the ethanol, the mix-ture is poured into water and is extracted with ethyl ether; after anhydrifying on Na2SO4, the solvent is evaporated at reduced pressure. The product is puri-fied by means of distillation (T = 125 C; P = 1 mmHg).
50 g of monosubstituted diethylmalonate are thus ob-tained.
50 g of monosubstituted diethylmalonate dissolved in 75 ml of ethanol are added to the solution of KOH
in 75 ml of water. The mixture is stirred for 4 hours at 80 C. After removing the ethanol by evaporation at reduced pressure, the mixture is acidified with HC1 (1:1) and extracted with ethyl acetate. After washing the organic extracts to neutrality and anhydrifying on Na2SO91 the solvent is evaporated under vacuum. 37.4 g of monosubstituted malonic acid are obtained.
The diacid, thus obtained, decarboxylates in 1 hour, at 160 C. 31.6 g of mono-acid are obtained.
SOC12 is added to the acid, dropwise. The mixture is stirred for 12 hours. The acyl chloride is isolated after removing the excess thionyl chloride by means of distillation under vacuum. 31.0 g of acyl chloride are obtained.
The acyl chloride dissolved in 50 ml of methylene chloride is added, at 10 C, to the suspension of A1C13 in 400 ml of methylene chloride. The mixture is stirred for 1 hour at room temperature. It is poured into ice and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated under vacuum. 22.0 g of product are obtained (total yield = 260).
O OH
NaBH4 O
22.0 g (150.7 mmoles) of 4-methyl-l-indanone 3.9 g (102.6 mmoles) of sodium boronhydride 88 ml of tetrahydrofuran 44 ml of methanol NaBH4 is added, in portions, at 0 C, to the solu-tion of 4-methyl-l-indanone in THF/CH3OH. After 3 hours the mixture is poured into water and extracted with ether. After washing the organic extracts to neutral-ity and anhydrifying on Na2SO4, the solvent is evapo-rated under vacuum. 22.0 g of 4-methyl-i-indanol are obtained (yield = 99%).
H OOEt H
o --~ o 22 g (148.6 mmoles) of 4-methyl-l-indanol 123 ml (307 mmoles) of n-butyl-lithium 2.5 M solution in hexane 750 ml of hexane 39.1 ml (322 mmoles) of diethylcarbonate N-butyl-lithium is added, at 0 C, to the solution of 4-methyl-l-indanol in hexane. The mixture is stirred for 2 hours at 60 C. Diethylcarbonate is added dropwise, at -70 C. The mixture is left to rise to room temperature. After 8 hours it is poured into water and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated. After purification on a silica gel chromatographic column (eluant hex-ane/ethyl acetate =9/1), 6.9 g of product are obtained (yield = 21.2%) OOEt OOEt H
12.5 g (56.8 mmoles) of hydroxy ester 400 mg (2.1 mmoles) of p-toluenesulfonic acid (PTSA) 100 of toluene.
PTSA is added to the toluene solution of hydroxy ester. The mixture is stirred at boiling point, remov-ing the azeotropic mixture/toluene by distillation.
After 2 hours the mixture is washed until neutrality with a saturated solution of NaHCO3 and anhydrified on Na2SO4, and the solvent is evaporated. 10.0 g of prod-uct are thus obtained (yield = 870).
OOEt OH
LiAIH4 o --~ o 10.0 g (49.5 mmoles) of ester 1.1 g (28.9 mmoles) of lithium aluminum hydride 200 ml of ethyl ether The ester dissolved in 60 ml of ethyl ether is added, at -30 C, by means of a drip funnel, to the suspension in ethyl ether of LiAlH9. After 30 minutes water is slowly added, at 0 C, and then HC1 (2N); the mixture is extracted with ethyl ether. After washing the organic extracts __ ___-____ity and anhydrifying on Na2SOq1 the solvent is evaporated at reduced pressure.
7.8 g of alcohol are obtained (yield = 99%).
H Br O \ -~ O \
8.8 g (55 mmoles) of alcohol 1.77 ml (18.15 mmoles) of phosphorous tribromide 110 ml of inethylene chloride.
PBr3 is added dropwise, at -20 C, to the solution of alcohol in CH2C12. After 30 minutes a saturated aqueous solution of NaHCO3 is slowly added until basic pH. The mixture is extracted with ethyl ether and is washed to neutrality with water. After anhydrifying on Na2SO4 and evaporating the solvent, 7.8 g of product are obtained (yield = 64%).
Preparation of 4,7-dimethyl-indenyl-lithium O
+ ci A1C13 CH2C12 Cl H2S04 cl H; H3 14.5 g (137 mmoles) of p-xylene 16 g of A1C13 ml (104.7 mmoles) of 3-chloropropionyl chloride 5 70 ml of methylene chloride 90 ml of conc. HZS09.
A solution of 3-chloro propionyl chloride in xy-lene is dripped in about 1 hour into a suspension of A1C13 in methylene chloride maintained at 0 C in an in-10 ert atmosphere. At the end of the addition the mixture is left to rise to 10 C and is maintained at 10-20 C
for about 2 hours. It is poured into ice and extracted with methylene chloride. The organic extracts are washed with water until neutrality and then dried on sodium sulfate.
The residue obtained by evaporation of the sol-vent is added to H2SO4 at such a rate as to maintain the temperature between 20 and 30 C. At the end of the addition the mixture is brought to 80 C and maintained at this temperature for 2 hours. The mixture is then poured into ice and is extracted with ethyl ether.
ether solution is washed to neutrality with a satu-rated solution of sodium bicarbonate and then water, and is dried on sodium sulfate. The solid obtained by evaporation of the ether is washed with petroleum ether and dried. 20 g of 4,7-dimethyl-l-indanone are thus obtained (91% of yield in the two passages).
UAHH4 PT-~
0 ---~ ~ TT-IF
2.9 g (18.1 mmoles) of 4,7-dimethyl-l-indanone 0.35 g (9.2 inmoles) of LiAlH4 30 ml of ethyl ether 10 ml of THF
0.2 g (1.05 mmoles) of p-toluenesulfonic acid (PTSA).
Indanone is slowly added to the suspension of LiAlH4 maintained at -30 C in an inert atmosphere. After 30 minutes the reaction is completed. Ice and HC1 2N are carefully added, the mixture is then extracted with ethyl ether and washed to neutrality, dried on sodium sulfate and evaporated. The indanol obtained is dis-solved in 10 ml of THF, p-toluenesulfonic acid is added and the mixture is brought to reflux temperature for 1 hour. Solid NaHCO3 and Na2SO4 are added_ The mix-ture is filtered and the solvent evaporated obtaining 2.4 g of 4,7-dimethylindene (91% yield).
I,i n-BuI i O
Br 4,7-Merindenillitio 7.4 g (51.4 mmoles) of 4,7-dimethyl-indene 32.3 ml (51.6 mmoles) of LiBu 1.6 M solution in hexane 7.8 g (35.1 mmoles) of benzyl bromide 297 ml of tetrahydrofuran 148 ml of hexane LiBu is added to the solution in THF and hexane of 4,7-dimethyl-indene. After 2 hours, the bromide dissolved in 20 ml of THF and 10 ml of hexane is added, at -70 C. The mixture is left to rise to room temperature, after 8 hours water is added and the mix-ture is extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated. 3.1 g of product are obtained, after purification on a silica gel column using hexane/ethyl acetate as eluant in a ratio of 98/2 (yield = 310).
Synthesis of 4-methylene(2-indenyl)indene Li(N-isoPrz) Li+
O
r O
S~fr.j bfe lvfe ~
l Me vte MqSi ~ Me Ph Ph Ph Ph 1de Ph Ph Table 1: Examples of structures of compounds with general formula (I) The compounds having general formula (Ia) can be prepared by means of a simple and original process which is illustrated in Scheme 1 below.
O Et 0 Et OH ~li td OH
a b -~ -r -~
R RI _ Ri RZ RI
d RS
R, R, R6 R9 r ~ H
Rg-3 f Rg ~---RZ Ri R Ri R Rt (Vin (vn c~) Scheme 1 a = LiBu(Zeq.)/hexane; b = diethylcarbonate; c =
PTSA/toluene; d = LiAlH4 or LiR or RMgX; e = PBr; f Li (C5HR3R9R5R6) In particular said process comprises the follow-ing steps:
(a) reaction of 1-indanol derivatives having formula (II), wherein the R1 and R2 groups have the meaning de-fined above, with LiBu to give the double salt having formula ( I I I ) ;
(b) reaction of the double lithium salt having for-mula (III), obtained in step (a), with electrophilic reagents, such as diethyl carbonate, to obtain hydroxy ester (IV);
(c) dehydration reaction of the alcohol function of the hydroxyester having formula (IV), obtained in step (b), carried out in an acid environment to give the ester (V) ;
(d) reduction reaction of the ester having formula (V), obtained in step (c), to obtain the alcohol (VI);
(e) bromination reaction of the alcohol having for-mula (VI) to give the bromine derivative (VII);
(f) formation reaction of the indenyl derivative hav-ing formula (Ia), starting from the bromine derivative having formula (VII) obtained in step (e) and from lithium salts of cyclopentadienyl anions, whose corre-sponding neutral derivative can be represented by the following general formula (VIII):
R;
R,4.
(vIIM
wherein each substituent R3, R4, R5 and R6 has the mean-ings defined above.
Step (a) of the process of the present invention is described in Chem. Ber. (1980) 113, 1304.
In particular, this article discloses that some benzyl alcohols and other phenyl carbinols, among which 1-indanol (Synthesis (1981) 59) can be deproto-nated in the presence of LiBu/tetramethylenediamine in pentane to give lithium(ortho-lithium)alkoxides.
The reaction described in step (a) can be carried out in the presence of base reagents such as, for ex-ample, lithium butyl, lithium methyl, sodium hydride in hydrocarbon and/or ether solvents or their mixtures at temperatures ranging from -30 to 120 C; the pre-ferred conditions comprise the use of lithium butyl in hexane at temperatures ranging from 0 to 70 C.
Typical 1-indanols having general formula (II) are 1-indanol, 2-methyl-l-indanol, 3-methyl-l-indanol, 3-ethyl-l-indanol, 4-methyl-l-indanol.
One of the advantages of the process of the pres-ent invention consists in the fact that many 1-indanol derivatives are available on the market or can be eas-ily prepared by means of well-known acyla-tion/alkylation reactions of aromatic rings suitably substituted.
Step (b) of the process of the present invention comprises the reaction of the double lithium salt, having general formula (III), with electrophilic rea-gents among which diethyl carbonate, dimethyl carbon-ate, carbon dioxide, ethyl chloroformiate, are par-ticularly appropriate for the purpose, in hydrocarbon and/or ether solvents or their mixtures at tempera-tures ranging from -100 to 120 C, preferably with di-ethyl carbonate in hexane at temperatures ranging from -70 to 25 C.
Step (c) of the process of the present invention consists in the dehydration of the hydroxy ester (IV) to obtain the corresponding indenyl derivative having general formula (V).
This reaction can be carried out in the presence of strong acids such as HC1, H2SO4, paratoluenesulfonic acid or blander dehydrating agents such as, for exam-ple, silica gel.
The choice of solvent for this reaction is very wide as it is possible to successfully use apolar sol-vents such as aliphatic hydrocarbons, medium polar solvents such as aromatic hydrocarbons or polar sol-vents such as ethers or chlorinated hydrocarbons; the temperature at which the reaction can take place can also be selected within a very wide range, typically from 25 to 150 C and the selection generally depends not only on the substrate, but also on the type of solvent used, preferably paratoluenesulfonic acid in toluene is used at temperatures ranging from 50 to 110 C.
Step (d) of the process of the present invention comprises the reduction of the ester group to alcohol with the formation of the compound having general for-mula (VI); this reduction can be carried out with various reagents among which LiAlH4, NaBH4, NaH, MgH2, LiBu, LiMe, MeMgCl, PhMgBr, ButMgCl, generally in ether solvents, but it is also possible to use alternative solvents having other characteristics, at temperatures ranging from -70 to 100 C; LiAl4 in ethyl ether is preferably used at temperatures ranging from -30 to 25 C.
Step (e) of the process of the present invention comprises the bromination of the alcohol function to give the bromine derivative having general formula (VII); also in this case there are various synthetic alternatives, well known to experts in the field, which comprise the use of various brominating agents in different solvents; the preferred conditions com-prise the use of PBr3 in methylene chloride at tempera-tures ranging from -20 to 25 C.
Step (f) of the process of the present invention, comprises the reaction of a cyclopentadienyl anion with the bromine derivative having general formula (VII), obtained by the reaction of the corresponding neutral derivative, having general formula (VIII), with a suitable base.
Experts in the field know that there is a wide variety of products capable of satisfying this re-quirement; it is in fact possible to use alkyls or hy-drides of electro-positive metals such as, for exam-ple, lithium methyl, lithium butyl, lithium ter-butyl, magnesium dibutyl, sodium hydride, potassium hydride, magnesium hydride, the well-known Grignard reagents:
RMgX, or also the alkaline or earth-alkaline metals themselves or their alloys.
All the reagents are generally easy to find on the market, with acceptable costs, and consequently their selection frequently depends on the type of sub-strate whose anion is to be obtained.
The solvents for effecting this reaction can be selected from aliphatic or aromatic hydrocarbons, ethers and/or their mixtures, the preference of one or the other often depending on the particular demands of solubility or reaction rate of the case in question.
The temperatures at which the reaction is carried out can vary within a very wide range, typically from -80 to 110 C and essentially depend on the thermal stability of the substrates and on the solvent used.
The preferred conditions for obtaining the anions of the compound having general formula (VIII) comprise the use of lithium butyl in mixtures of hexane/THF at temperatures ranging from 00 to 60 C.
Typical compounds having general formula (VIII) are: cyclopentadiene, methyl-cyclopentadiene, tetrame-thyl-cyclopentadiene, trimethylsilyl-cyclopentadiene, indene, 3-meth-yl-indene, 4,7-dimethyl-indene, 5,6-dimethyl-indene, 4,5,6,7-tetrahydro-indene, 4,5,6,7-tetrahydro-2-methyl-ind-ene, 2,4,5,6,7,8-hexahydro-azulene, 2-methyl-2,4,5,6,7,8-hexahydro-azulene, 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyc-lo-octene, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13-decahydro-2H-cyclopen-tacyclododecene, fluorene, 1,2,3,4,5,6,7,8-octa-hydro-fluo-rene.
In the preferred embodiment, the compound having general formula (VIII) is cyclopentadiene, tetrame-thyl-cyclopentadiene, indene, 3-methyl-indene, 4,7-dimethyl-indene, 2,4,5,6,7,8-hexahydro-azulene, fluo-rene.
In an even more preferred embodiment the compound having general formula (VIII) is indene, 4,7-dimethyl-indene.
This reaction can be carried out in a wide vari-ety of solvents selected from aromatic and/or ali-phatic hydrocarbons and from ethers and/or their mix-tures, at a temperature ranging from -80 to 120 C.
There are no particular limitations in the order of addition of the various reagents, but it is preferable to operate by adding the bromine derivative (VII), ei-ther pure or diluted in ether solvent, to the solu-tion/suspension containing the cyclopentadienyl anion, obtained as described above, at temperatures ranging from -70 to 25 C.
Alternatively, step (f) of the process of the present invention can be carried out by reacting the brominated product (VII) with a suitable lithium eno-late giving rise to the formation of indenyl-cyclopentadienyl products having general formula (XIII) :
R!
Rg R, R
RIo Ri i GXIIn wherein:
- R1 and R2 can independently occupy any of the free positions of the indene group;
- Rl, R2, R7, R8, R9, Rio and Rll independently repre-sent hydrogen, halogen, preferably F, Cl or Br, a linear or branched C1-C2o hydrocarbyl group, satu-rated or unsaturated, cycloaliphatic or aromatic, or a C1-C2o hydrocarbyl group substituted with one or more halogen atoms, or a C1-C2o hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, pref-erably Si, 0, N, S, P, or, wherein any two of the substituents R9r Rlo and Rll, adjacent to each other, are joined to each other to form a satu-rated or unsaturated C4-C20 cyclic structure, com-prising a bond of the cyclopentadienyl ring, said structure optionally containing one or more of the heteroatoms specified above;
- R12 can be independently hydrogen, a linear or branched C1-C20 hydrocarbyl group, saturated or un-saturated, cycloaliphatic or aromatic, or a C1-C20 hydrocarbyl group comprising one or more heteroa-toms of groups 14 to 16 of the periodic table of elements, preferably Si, 0, N, S, P.
The variant in step (f) of the process of the present invention is indicated in Scheme 2:
9 Li Li O
Rto Rto Rto Ri t Rti Rt t (IX) (Xa) (Xb) h Ri Ri Rt R7 R~ R~
Rs R2 Rs R2 Rs RZ
Rg Rtz 41 OH
Rto Rto R12 Rto Rt t Ri i Rt i CA= (XII) (X) 15 Scheme 2 g:Li[N(iso-Pr)2/THF/-78 C,h:(VII)/THF;i:NaBH4 or LiR12 or R,2MgX;1:CuSO4/ toluene/110 C.
In accordance with this, a further object of the present invention relates to a variant of the process 20 for the preparation of compounds having general for-mula (Ia), which gives rise to the formation of analo-gous products having general formula (XIII) wherein the substituents R1, Rzr R7, R8, Rg, Rlo, Rll and R12 have the meaning defined above, which comprises the follow-25 ing steps:
(g) reaction of a cyclic ketone, having general for-mula (IX), wherein the groups R9r Rlo and R11 have the meaning defined above, with a lithium amide to give the mixture of anions having general formula (Xa) / (Xb) ;
(h) reaction of the mixture of anions (Xa)/(Xb) with the brominated product having general formula (VII), prepared according to what is indicated above (Scheme 1) ;
(i) reduction of the functional carbonyl group to al-cohol, by means of suitable reagents, with the forma-tion of the derivative having general formula (XII), wherein the R12 group has the meaning defined above;
(1) dehydration of the derivative having general for-mula (XII), obtained in step (i), with the formation of the desired indenyl-cyclopentadienyl compound, hav-ing general formula (XIII), wherein the groups R1r R2, R7, Rer R9, Rlo, Rll and R12 have the meaning defined above.
In step (g) a cyclic ketone having general for-mula (IX) is reacted with a strong non-alkylating base, in ether solvents such as ethyl ether, tetrahy-drofuran, dioxane, as the dissolving capacity of the latter can improve the reaction kinetics, but this does not mean that less polar solvents, such as aro-matic and/or aliphatic hydrocarbons, can also be con-veniently used for the purpose, at temperatures rang-ing from -80 C to 110 C, the selection of the latter depending on the type of solvent and substrates used.
Typical strong bases, suitable for the purpose, are alcoholates of alkaline and earth-alkaline metals such as for example lithium methoxide, sodium methox-ide, sodium ethoxide, sodium iso-propoxide, potassium ter-butoxide, magnesium di-ethoxide, etc. or the rela-tive amides such as, for example, lithium amide, so-dium amide, lithium di-ethylamide, lithium di-isopropylamide, lithium bis-(trimethylsilyl)amide, po-tassium di-butylamide, etc.
In the preferred embodiment the strong bases are selected from lithium methoxide, sodium ethoxide, po-tassium ter-butoxide, sodium amide, lithium di-isopropylamide.
In an even more preferred embodiment the strong base is lithium di-isopropylamide.
Typical cyclic ketones having general formula (IX), suitable for being used in step (g) of Scheme 2 are: cyclopent-l-en-3-one, 1-methyl-cyclopent-l-en-3-one, 1,2,5-tri-methyl-cyclopent-l-en-3-one, indan-l-one, 3-methyl-indan-l-one, 4,7-dimethyl-indan-l-one, indan-2-one, etc.
In the preferred embodiment the cyclo-ketone com-pound having general formula (IX) is selected from cy-clopent-l-en-3-one, 1,2,5-trimethylcyclopent-l-en-3-one, indan-l-one, 3-methyl-indan-l-one; in an even more preferred embodiment compound (IX) is indan-l-one.
Step (h) of the process of the present invention consists in the reaction between the mixture of anions (Xa)/(Xb) with the brominated product (VII), prepared according to Scheme 1, which can be carried out in hy-drocarbon, ether solvents or their mixtures, the use of the same solvent adopted in the previous step (g), at temperatures ranging from -80 C to 70 C, normally being preferred.
In a preferred embodiment, the reaction is car-ried out in a mixture of THF/hexane at temperatures ranging from -70 to 25 C.
Step (i) of the process of the present invention consists in a reduction of the functional carbonyl group, present in the derivative having general for-mula (XI), to alcohol, with the formation of the com-pound having general formula (XII). There are various possibilities, well known to experts in the field, for selecting the reducing reagents suitable for the pur-pose, among which lithium aluminum hydride, sodium bo-ron hydride, sodium hydride, lithium methyl, lithium phenyl, ethyl magnesium bromide, isopropyl magnesium bromide, etc., which can be successfully used either in hydrocarbon or ether solvents or their mixtures, at temperatures ranging from -40 to 70 C. In a preferred embodiment, sodium boron hydride in tetrahydrofuran is used at temperatures ranging from -20 to 25 C.
Step (1) of the process of the present invention, consists in the dehydration of the derivative (XII), obtained in step (i), to give the desired indenyl-cyclopentadienyl product having general formula (XI I I ) .
The latter can be carried out in the presence of dehydrating agents such as, for example, silica gel, strong acids such as HC1, H2SO9, paratoluenesulfonic acid, or anhydrous inorganic salts such as, for exam-ple, Cu ( S04 ), Mg ( S09 ), Na (S04) 2, CaC12, etc.
The selection of the solvent for this reaction is very wide as it is possible to successfully use apolar solvents such as aliphatic hydrocarbons, medium polar solvents such as aromatic hydrocarbons or polar sol-vents such as ethers or chlorinated hydrocarbons; the temperature at which the reaction takes place can also be selected within a very wide range, typically from -20 to 130 C and the selection generally depends not only on the substrate but also on the type of solvent used. In a preferred embodiment anhydrous Cu(S09) is used in toluene at 110 C.
The processes of the present invention do not necessarily require the isolation of the single reac-tion products at the end of the respective steps.
In addition to the advantage of starting from products which are easily available, the processes comprise quite simple chemical passages and produce satisfactory overall yields.
The preparation of the complexes having general formula (I) can be carried out according to one of the well-known methods described in literature for the production of bridged bis-cyclopentadienyl complexes of transition metals.
The method most commonly used comprises reacting a salt of the metal M (preferably a chloride), with a salt of an alkaline metal of the dianion of the bis-cyclo-pentadienyl ligand having the desired structure.
The preparation of the complexes having formula (I) normally comprises two steps, in the first of which the ligand having general formula (Ia) is re-acted with a lithium alkyl, such as lithium methyl or lithium butyl, in an inert solvent, preferably con-sisting of an aromatic hydrocarbon or an ether, par-ticularly tetrahydrofuran or ethyl ether.
The temperature during the reaction is preferably maintained below room temperature to avoid the crea-tion of secondary reactions. At the end of the reac-tion the corresponding lithium salt of the cyclopenta-dienyl dianion is obtained.
In the second step, the salt of the cyclopentadi-enyl dianion is reacted with a salt, preferably a chloride, of the transition metal M, again in an inert organic solvent at a temperature preferably ranging from -30 to 70 C.
At the end of the reaction, the complex having formula (I) thus obtained is separated and purified according to the known methods of organometallic chem-istry.
As is known to experts in the field, the above operations are sensitive to the presence of air and humidity and should therefore be carried out in an in-ert atmosphere, preferably under nitrogen or argon.
Numerous general and specific methods which sub-stantially originate from the method indicated above, are described in literature, such as, for example in the publications of D.J. Cardin "Chemistry of Organo Zr and Hf Compounds" J. Wiley and Sons Ed., New York (1986); R. Haltermann "Chemical Review", vol. 92 (1992) pages 965-994; R.O. Duthaler and A. Hafner "Chemical Review", vol. 92 (1992) pages 807-832.
The metallocene compounds of the present inven-tion can be conveniently used as catalytic components for the polymerization of olefins.
A further object of the present invention there-fore relates to a catalyst for the polymerization of olefins comprising the reaction product between:
(A) a metallocene compound having formula (I) ob-tained as described above, and (B) one or more compounds capable of activating the metallocene (I) selected from those known in the art, particularly an organic derivative of an element M' different from carbon and selected from the elements of groups 1, 2, 12, 13 and 14 of the periodic table.
In particular, according to the present inven-tion, said element M' is selected from boron, alumi-num, zinc, magnesium, gallium and tin, more particu-larly boron and aluminum.
In a preferred embodiment of the present inven-tion, the component (B) is an organo-oxygenated de-rivative of aluminum, gallium or tin. This can be de-fined as an organic compound of M' , in which the lat-ter is bound to at least one oxygen atom and to at least one organic group consisting of an alkyl group having from 1 to 12 carbon atoms, preferably methyl.
According to this aspect of the invention, compo-nent (B) is more preferably an aluminoxane. -As is known, aluminoxanes are compounds containing Al-O-Al bonds, with a varying O/Al ratio, which can be ob-tained, under controlled conditions, by the reaction of an aluminum alkyl or aluminum alkyl halide, with water or other compounds containing pre-established quantities of water available, such as, for example, in the case of the reaction of aluminum trimethyl with aluminum sulfate hexahydrate, copper sulfate pentahy-drate or iron sulfate pentahydrate.
Aluminoxanes preferably used for the formation of the polymerization catalyst of the present invention are oligo- poly-meric, cyclic and/or linear compounds, characterized by the presence of repetitive units hav-ing the following formula:
wherein R13 is a C1-C12 alkyl group, preferably methyl.
Each dialuminoxane molecule preferably contains from 4 to 70 repetitive units which may also not all be equal to each other, but contain different R13 groups.
When used for the formation of a polymerization catalyst according to the present invention, the alu-minoxanes are put in contact with a complex having formula (I) in such proportions that the atomic ratio between Al and the transition metal M is within the range of 10 to 10000 and preferably from 100 to 5000.
The sequence with which the complex (I) and the alu-minoxane are put in contact with each other, is not particularly critical.
In addition to the above aluminoxanes, the defi-nition of component (B) according to the present in-vention also comprises galloxanes (in which, in the previous formulae, gallium is present instead of alu-minum) and stannoxanes, whose use as cocatalysts for the polymerization of olefins in the presence of met-allocene complexes is known, for example, from patents US 5,128,295 and US 5,258,475.
According to another preferred aspect of the pre-sent invention, said catalyst can be obtained by put-ting component (A) consisting of at least on complex having formula (I), in contact with component (B) con-sisting of at least one compound or a mixture of or-ganometallic compounds of M' capable of reacting with the complex having formula (I), extracting from this a 6-bound group R' to form, on the one hand at least one neutral compound, and on the other hand an ionic com-pound consisting of a metallocene cation containing the metal M and an organic non-coordinating anion con-taining the metal M', whose negative charge is delo-calized on a multicenter structure.
Components (B) suitable as ionizing systems of the above type are preferably selected from the volu-minous organic compounds of boron and aluminum, such as for example, those represented by the following general formulae:
[ (Rc) xNH4-x] + [B (RD) 4 ] : B (RD) 3 : [Ph3C] + [B (RD) 4 ] i [(Rc)3PH]+[B(RD)4] : [Li]+[B(RD)4] : [Li]+[Al(RD)4] ;
wherein the deponent "x" is an integer ranging from 0 to 3, each Rc group independently represents an alkyl or aryl radical having from 1 to 12 carbon atoms and each RD group independently represents an aryl radical partially or, preferably, totally fluorinated, having from 6 to 20 carbon atoms.
Said compounds are generally used in such quanti-ties that the ratio between the atom M' of component (B) and the atom M of component (A) is within the range of 0.1 to 15, preferably from 0.5 to 10, more preferably from 1 to 6.
Component (B) can consist of a single compound, normally an ionic compound, or a combination of this compound with MAO, or, preferably, with an aluminum trialkyl having from 1 to 16 carbon atoms in each al-kyl residue, such as for example A1Me3, AlEt3, A1(i-Bu)3.
In general, the formation of the ionic metallo-cene catalyst, in accordance with the present inven-tion, is preferably carried out in an inert liquid me-dium, more preferably hydrocarbon. The selection of components (A) and (B) which are preferably combined with each other, as well as the particular method used, can vary depending on the molecular structures and result desired, according to what is described in detail in specific literature available to experts in the field.
Examples of these methods are qualitatively sche-matized in the list provided hereunder, which however does not limit the overall scope of the present inven-tion:
(i) by contact of a metallocene having general for-mula (I) wherein at least one, preferably both, of the substituents X1 and X2 is hydrogen or an alkyl radical, with an ionic compound whose ca-tion is capable of reacting with one of the substituents X1 or X2 to form a neutral com-pound, and whose anion is voluminous, non-coordinating and capable of delocalizing the negative charge;
(ii) by the reaction of a metallocene having the previous formula (I) with an alkylating agent, preferably an aluminum trialkyl, used in molar excess of 10/1 to 500/1, followed by the reac-tion of a strong Lewis acid, such as for exam-ple, tris(pentafluo-rophenyl)boron a in more or less stoichiometric quantity or in slight ex-cess with respect to the metal M;
(iii) by contact and reaction of a metallocene having the previous formula (I) with a molar excess of 10/1 to 1000/1, preferably from 30/1 to 500/1 of an aluminum trialkyl or an alkylaluminum halide or one of their mixtures, which can be represented by the formula AlR,,X3-,n, wherein R
is a linear or branched C1-C1Z alkyl group, X is a halogen, preferably chlorine or bromine, and "m" is a decimal number ranging from 1 to 3;
followed by the addition to the composition thus obtained, of at least an ionic compound of the type described above in such quantities that the ratio between B or Al and the atom M
in the metallocene complex is within the range of 0.1 to 20, preferably from 1 to 6.
Examples of ionizing ionic compounds or multicomponent reactive systems capable of producing an ionic cata-lytic system by reaction with a metallocene complex, according to the present invention, are described in the following patent publications, whose content in herein incorporated as reference:
= European patent application, published under the Nr.: EP-A 277,003, EP-A 277,004, EP-A 522,581, EP-A 495,375, EP-A 520,732, EP-A 478,913, EP-A
468,651, EP-A 427,697, EP-A 421,659, EP-A
418,044;
= International patent applications published under the Nr.: WO 92/00333, WO 92/05208; WO 91/09882;
= Patents U.S. 5,064,802, U.S. 2,827,446, U.S.
5, 066, 739.
Also included in the scope of the present inven-tion are those catalysts comprising two or more com-plexes having formula (I) mixed with each other. Cata-lysts of the present invention based on mixtures of complexes having different catalytic activities can be advantageously used in polymerization when a wider mo-lecular weight distribution of the polyolefins thus produced is desired.
According to an aspect of the present invention, in order to produce solid components for the formation of catalysts for the polymerization of olefins, the above complexes can also be supported on inert solids, preferably consisting of oxides of Si and/or Al, such as for example, silica, alumina or silica-aluminates.
For the supporting of said catalysts, the known supporting techniques can be used, normally comprising contact, in a suitable inert liquid medium, between the carrier, optionally activated by heating to tem-peratures exceeding 200 C, and one or both of compo-nents (A) and (B) of the catalyst of the present in-vention. For the purposes of the present invention, it is not necessary for both components to be supported, as it is also possible for only the complex having formula (I) or the organic compound of B, Al, Ga or Sn as defined above, to be present on the surface of the carrier. In the latter case, the component which is not present on the surface is subsequently put in con-tact with the supported component, at the moment of the formation of the catalyst active for the polymeri-zation.
Also included in the scope of the present inven-tion are the complexes, and catalytic systems based on these, which have been supported on a solid by means of the functionalization of the latter and formation of a covalent bond between the solid and a metallocene complex included in formula (I) above.
A particular method for the formation of a sup-ported catalyst according to the present invention comprises pre-polymerizing a relatively small fraction of monomer or mixture of monomers in the presence of the catalyst, so as to include this in a solid micro-particulate, which is then fed to the actual reactor itself for completing the process in the presence of an additional olefin(s). This provides a better con-trol of the morphology and dimensions of the polymeric particulate obtained at the end.
One or more other additives or components can be optionally added to the catalyst according to the pre-sent invention, as well as the two components (A) and (B), to obtain a catalytic system suitable for satis-fying specific requisites. The catalytic systems thus obtained should be considered as being included in the scope of the present invention. Additives or compo-nents which can be included in the preparation and/or formulation of the catalyst of the present invention are inert solvents such as, for example, aliphatic and/or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly co-ordinating additives (Lewis bases) selected, for example, from non-polymerizable olefins, ethers, tertiary amines and alcohols, halogenating agents such as silicon halides, halogenated hydrocar-bons, preferably chlorinated, and the like, and again all other possible components normally used in the art for the preparation of the traditional homogeneous catalysts of the metallocene type for the (co)polymerization of olefins.
Components (A) and (B) form the catalyst of the present invention by contact with each other, prefera-bly at temperatures ranging from 200 to 60 C and for times varying from 10 seconds to 1 hour, more prefera-bly from 30 seconds to 15 minutes.
The catalysts according to the present invention can be used with excellent results in substantially all known (co)polymerization processes of olefins, ei-ther in continuous or batchwise, in one or more steps, such as, for example, processes at low (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa) pressure, at temperatures ranging from 10 to 240 C, optionally in the presence of an inert diluent. Hydrogen can be con-veniently used as molecular weight regulator.
These processes can be carried out in solution or suspension in a liquid diluent normally consisting of an aliphatic or cycloaliphatic saturated hydrocarbon, having from 3 to 20 carbon atoms or a mixture of two or more of these, but which can also consist of a monomer as, for example, in the known co-32 ' polymerization process of ethylene and propylene in liquid propylene. The quantity of catalyst introduced into the polymerization mixture is preferably selected so that the concentration of the metal M ranges from 10-9 to 10-$ moles/liter.
Alternatively, the polymerization can be carried out in gas phase, for example, in a fluid bed reactor, normally at pressures ranging from 0.5 to 5 MPa and at temperatures ranging from 50 to 150 C.
According to a particular aspect of the present invention, the catalyst for the (co) polymerization of ethylene with other olefins is prepared separately (preformed) by contact of components (A) and (B), and is subsequently introduced into the polymerization en-vironment.
The catalyst can be first charged into the polym-erization reactor, followed by the reagent mixture containing the olefin or mixture of olefins to be po-lymerized, or the catalyst can be charged into the re-actor already containing the reagent mixture, or fi-nally, the reagent mixture and the catalyst can be contemporaneously fed into the reactor.
According to another aspect of the present inven-tion, the catalyst is formed "in situ", for example by introducing components (A) and (B) separately into the polymerization reactor containing the pre-selected olefinic monomers.
The catalysts according to the present invention can be used with excellent results in the polymeriza-tion of ethylene to give linear polyethylene and in the copolymerization of ethylene with propylene or higher olefins, preferably having from 4 to 12 carbon atoms, to give copolymers having different charaCter-istics depending on the specific polymerization condi-tions and on the quantity and structure of the comono-mer used.
For example, linear polyethylenes can be ob-tained, with a density ranging from 0.880 to 0.940, and with molecular weights ranging from 10,000 to 2,000,000. The olefins preferably used as comonomers of ethylene in the production of low or medium density linear polyethylene (known with the abbreviations ULDPE, VLDPE and LLDPE depending on the density), are 1-butene, 1-hexene and 1-octene.
The catalyst of the present invention can also be conveniently used in copolymerization processes of ethylene and propylene to give saturated elastomeric copolymers vulcanizable by means of peroxides and ex-tremely resistant to aging and degradation, or in the terpolymerization of ethylene, propylene and a diene, generally non-conjugated, having from 4 to 20 carbon atoms, to obtain vulcanizable rubbers of the EPDM
type.
In the case of these latter processes, it has been found that the catalysts of the present invention allow the production of polymers having a particularly high comonomer content and average molecular weight under the polymerization conditions.
In the case of the preparation of EPDM, the di-enes which can be used for the purpose are preferably selected from:
= linear chain dienes such as 1,4-hexadiene and 1,6-octadiene;
= branched dienes such as 5-methyl-l,4-hexadiene;
3,7-dimethyl-l,6-octadiene; 3,7-dimethyl-1,7-octadiene;
= dienes with a single ring such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene; 1,5-cyclododecadiene;
= dienes having bridged condensed rings such as di-cyclopentadiene; bicyclo[2.2.1]hepta-2,5-diene;
alchenyl, alkylidene, cycloalkenyl and cycloalky-lidene norbornenes such as 5-methylene-2-norbornene, 5-ethylidene-2-borbornene (ENB), 5-propenyl-2-norbornene.
Among the non-conjugated dienes typically used for preparing these copolymers, dienes containing at least one double bond in a stretched ring are pre-ferred, even more preferably 5-ethylidene-2-norbornene (ENB), and also 1,4-hexadiene and 1,6-octadiene.
In the case of EPDM terpolymers, it is convenient for the quantity of dienic monomer not to exceed 15%
by weight, and it is preferably from 2 to 10% by weight. The propylene content on the other hand ranges from 20 to 55% by weight.
The catalysts of the present invention can also be used in homo- and co-polymerization processes of olefins according to the known techniques, giving, with excellent yields, atactic, isotactic or syndio-tactic polymers, depending on the structure and geome-try of the metallocene complex having formula (I).
Olefins suitable for the purpose are those having from 3 to 20 carbon atoms, optionally also comprising halogens and/or other heteroatoms or aromatic nuclei such as, for example, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-l-pentene, 1-decene and styrene.
The present invention is further described by the following examples, which, however, are provided for purely illustrative purposes and do not limit the overall scope of the invention itself.
CHARACTERIZATION METHODS
The analytical techniques and characterization methods used in the examples are listed below and are briefly described.
The characterization by means of NMR spectroscopy mentioned in the following examples was carried out on a nuclear magnetic resonance spectrometer mod. Bruker MSL-300, using, unless otherwise specified, CDC13 as solvent for each sample.
The molecular weight measurement of the olefinic polymers was carried out by means of Gel-Permeation Chromatography (GPC). The analyses of the samples were effected in 1,2,4-trichlorobenzene (stabilized with Santonox) at 135 C with a WATERS 150-CV chromatograph using a Waters differential refractometer as detector.
The chromatographic separation was obtained with a set of -Styragel HT columns (Waters) of which three with pore dimensions of 103, 109, 105 A respectively, and two with pore dimensions of 106 A, establishing a flow-rate of the eluant of 1 ml/min. The data were obtained and processed by means of Maxima 820 software version 3.30 (Millipore); the number (Mõ) and weight (Mw) aver-age molecular weight calculation was carried out by universal calibration, selecting polystyrene standards with molecular weights within the range of 6,500,000-2,000, for the calibration.
The determination of the content of units deriv-ing from propylene and possible diene in the polymers is carried out (according to the method of the Appli-cant) by means of IR on the same polymers in the form of films having a thickness of 0.2 mm, using an FTIR
Perkin-Elmer spectrophotometer model 1760. The inten-sity of the characteristic peaks is measured, of pro-pylene at 4390 cm 1 and ENB at 1688 ciri 1 respectively, in relation to the peak at 4255 cm"1, and the quantity is determined using a standard calibration curve.
The Melt Flow Index (MFI) of the polymers is de-termined in accordance with the regulation ASTM D-1238 D.
The Mooney viscosity (1+4) is determined at 100 C
using a Monsanto "1500 S" viscometer according to the method ASTM D 1646/68.
Synthesis of 1-methyl-4-methylene(1-indenyl)indene The following products are reacted:
170 ml of benzene 22.7 g (264 mmoles) of crotonic acid 106 g (795.2 mmoles) of aluminum trichloride o + ~ -~
The solution of crotonic acid in 100 ml of ben-zene is added dropwise to the suspension of A1C13 in 70 ml of benzene. The mixture is stirred at 80 C for 5 hours. It is poured into ice and is extracted with ethyl ether. After washing until neutrality with a saturated aqueous solution of NaHCO3 and water and an-hydrifying on Na2SO4, the solvent is evaporated. The product is purified by distillation (Tboil. = 125 C) 32.0 g are obtained (yield = 830).
32.0 g (219.2 mmoles) of 3-methyl-l-indanone, ob-tained in the previous step, are reacted with:
5.6 g (147 mmoles) of sodium boronhydride 128 ml of tetrahydrofuran 64 ml of methanol O OH
NaBH4 o -~
NaBH4 is added, in portions, to the solution of 3-methyl-l-indanone in tetrahydrofuran and methanol, at 0 C. After 2 hours the mixture is poured into ice and is extracted with ethyl ether. After washing the or-ganic extracts to neutrality with a saturated solution of NaCl and anhydrifying on Na2SO4, the mixture is fil-tered and the solvent evaporated. 30.8 g of product are obtained (95%).
14.8 g (0.1 moles) of 3-methyl-l-indanol, ob-tained in the previous step, are reacted with:
80 ml (0.2 moles) of LiBu 2.5 M in hexane 26.7 ml (0.22 moles) of diethylcarbonate 500 ml of hexane OH COOEt OH
1) LiBu 2) ~o N-butyl lithium is added, by means of a drip fun-nel, over a period of about 1 h, in an inert atmos-phere, to the suspension of 3-methyl-l-indanol in hex-ane, at 20 C. At the end of the addition the reaction mixture is heated to 60 C for 2 h, and, after cooling to -70 C, diethyl carbonate is then added. The tem-perature is left to rise slowly to 25 C and, after a further 8 h, the reaction mass is poured into water and is extracted with ethyl ether. The separated or-ganic phase is washed with water until neutrality, an-hydrified on sodium sulfate and the solvent is evapo-rated at reduced pressure. After purification on a silica gel column (eluant: hexane/ethyl acetate 9/1), 5.6 g of 3-methyl-7-carboethoxy-l-indanol are ob-tained.
5.6 g (25.45 mmoles) of 3-methyl-7-carboethoxy-l-indanol 80 ml of toluene 0.1 g (0.58 mmoles) of p-toluenesulfonic acid (PTSA) COOEt OH COOEt PTSA
Para-toluenesulfonic acid is added to the solu-tion of 3-methyl-7-carboethoxy-l-indanol in toluene.
The mixture is heated to 100 C and the water is re-moved by azeotropic distillation. After 2 h a satu-rated aqueous solution of NaHCO3 is added, the organic phase is separated, washed with water until neutrality and anhydrified on NaSO4. Finally the solvent is re-moved at reduced pressure and, after purification on a silica gel column (eluant: hexane/ethyl acetate 95/5), 5.0 g of 3-methyl-7-carboethoxy-l-indene are obtained.
5.0 g (24.7 mmoles) of 3-methyl-7-carboethoxy-l-indene 0.6 g (15. 8 mmoles ) of LiAlH4 100 ml of ethyl ether OH
COOEt L'A~a O Et20 O
A solution of 3-methyl-7-carboethoxy-l-indene in 40 ml of ethyl ether are added, at -30 C, to the sus-pension of LiAlHg in 60 ml of ethyl ether. The tempera-ture is slowly left to rise to 25 C and after 30 min water is slowly added and the mixture is acidified with HC1 2M. The reaction mass is extracted with ethyl ether, washed repeatedly with water until neutrality and dried on NaSO9. The solvent is finally removed un-der vacuum and 3.76 g of 7-(3-methylindenyl) methanol are obtained.
3.76 g (23.5 mmoles) of 7-(3-methylindenyl)methanol 2.1 g (7.86 mmoles) of PBr3 50 ml of methylene chloride OH Br O PBT3 0 ~
CH,C12 Phosphorous tribromide is slowly added, by means of a drip funnel, to the solution of 7-(3-methylindenyl) methanol in CH2C12, cooled to -20 C. The temperature is left to rise to 25 C and after 30 min a saturated aqueous solution of NaHCO3 is slowly added.
The reaction mass is extracted various times with ethyl ether, the organic extracts are washed with wa-ter until neutrality and dried on NaS09. After removing the solvent at reduced pressure, 4.9 g of 4-bromomethyl-l-methylindene are obtained.
7 g (31.4 mmoles) of 4-bromomethyl-l-methylindene, ob-tained in the previous step, are reacted with:
31 ml (77.5 mmoles) of LiBu 2.5 M in hexane 200 ml of THF
7.3 ml (62.3 mmoles) of indene CH2Br BuLi 00 co Li++ Ct11- CH2 Butyl lithium is added dropwise to the solution of indene in 100 ml of THF. The mixture is left under stirring for 2h at room temperature and is then cooled to -70 C. Bromine dissolved in THF is added. After 1 h at this temperature the mixture is left to rise to room temperature and is poured into water. It is ex-tracted with ethyl ether, the extracts are washed un-til neutrality and are anhydrified on sodium sulfate.
The residue obtained by evaporation of the solvent is purified on a silica gel column using petroleum ether as eluant. In this way 4.3 g of 1-methyl-4-methylene (1-indenyl)indene are obtained (53% yield).
Synthesis of 4-methylene(1-indenyl)indene The following products are reacted:
16.0 g (119.4 mmoles) of 1-indanol 100 ml (250 mmoles) of LiBu 2.5 M in hexane 31.5 (259.6 mmoles) of diethylcarbonate 500 ml of hexane OEt O
H LiBu w ~
^o ~o ^
N-butyl-lithium is added dropwise to the suspen-sion in 1-indanol in hexane, at -5 C. The mixture is stirred at 60 C for 2 hours and diethylcarbonate is added, at -70 C. The mixture is left to rise to room temperature. After 8 hours, it is poured into water and extracted with ethyl ether. After washing the or-ganic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated under vacuum. The product is purified by chromatographic separation on silica gel eluating with hexane and ethyl acetate in a ratio of 95/5. 6 g of product are obtained (yield=24.50).
g (24.3 mmoles) of hydroxy-ester, obtained in the previous step, are reacted with:
200 mg (1.05 mmoles) of para-toluenesulfonic acid 20 ml of toluene 5 EtO OEt0 H
O PTSA
--~ o The toluene solution of hydroxy ester and PTSA
are stirred at 90 C for 3 hours. The mixture is washed, until neutrality, with a saturated aqueous so-lution of NaHCO3 and with water. After anhydrifying the organic phase on Na2SO4 and filtering, the solvent is evaporated. The residue is purified on a silica gel chromatographic column with hexane and ethyl acetate as eluant in a ratio of 95/5. 4.0 g of ester are thus obtained (yield 87.7%).
8.8 g (46.8 mmoles) of ester, obtained in the previous step, are reacted with:
2.1 g (55.3 mmoles) of lithium aluminum hydride 120 ml of ethyl ether.
OEt O H
The ester dissolved in 20 ml of ethyl ether is added, at -20 C to the suspension, in ethyl ether, of LiAlH4. After 6 hours water is slowly added, the mix-ture is acidified with HC1 (2N) and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the mixture is filtered and the solvent evaporated. 6.6 g of alcohol are obtained (yield 96%).
6.6 g (45.2 mmoles) of alcohol, obtained in the previous step, are reacted with:
1.5 ml (15.82 mmoles) of phosphorous tribromide 70 ml of methylene chloride H Br \ PBr3 \
O --~ O
The phosphorous tribromide is added dropwise to the solution, in methylene chloride, of alcohol at -20 C. After 1 hour a saturated aqueous solution of NaHCO3 is added dropwise and the mixture is extracted several times with ethyl ether. After washing the or-ganic extracts to neutrality and anhydrifying on Na2SO4, the mixture is filtered and the solvent evapo-rated. 5.0 g of 4-bromomethyl-indene are obtained (yield 530) .
4.44 ml (33.6 mmoles) of inderie 15 ml (33.6 mmoles) of LiBu solution 2.5 M in hexane g (24 mmoles) of 4-bromomethyl-indene 90 ml of tetrahydrofuran 5 45 ml of hexane nBuLi DoU4 Br Indenyl-lithium o -~
N-butyl-lithium is added, at 5 C, to the solu-tion, in THF in hexane, of indene. After 1 hour, the mixture is cooled to -70 C and benzyl bromide dis-solved in 20 ml of THF is added. The mixture is left to rise to room temperature. After 8 hours, it is poured into water and is extracted with ethyl ether.
After washing the ether extracts to neutrality with water and anhydrifying on Na2SO4, the mixture is fil-tered and the solvent evaporated.
After purification on a silica gel chroma-tographic column (eluant: hexane), 2.3 g of 4-methylene(1-indenyl) indene are obtained (yield 39.3%) EXP,MPLE 3 Synthesis of 7-methyl-4-methylene(4,7-dimethyl-l-indenyl)-indene The following reaction scheme is followed:
OOEt COOEt EtONa/EtOH &--( + <OOEt Et OOEt ])KOH cJ_*_./cOOW. ~ ~Et 2)H+
~11OOH SOC12 ~OC1 A1C13 ~ 0 2 0 oci -Q\
108.0 g (583.7 mmoles) of o-methylbenzylbromide 150 ml (988 mmoles) of dimethylmalonate 21.4 g (930 mmoles) of sodium 350 ml of ethyl alcohol 25 g (445 mmoles) of KOH
30 ml of thionyl chloride 38 g (285.7 mmoles) of aluminum trichloride Metal sodium is added, in portions, to the etha-nol. Diethylmalonate is slowly added dropwise to the solution of sodium ethylate in ethanol, at 50 C, and then o-methyl-benzylbromide is added rapidly. The mix-ture is kept under stirring at boiling point for 2 hours. After evaporating most of the ethanol, the mix-ture is poured into water and is extracted with ethyl ether; after anhydrifying on Na2SO4, the solvent is evaporated at reduced pressure. The product is puri-fied by means of distillation (T = 125 C; P = 1 mmHg).
50 g of monosubstituted diethylmalonate are thus ob-tained.
50 g of monosubstituted diethylmalonate dissolved in 75 ml of ethanol are added to the solution of KOH
in 75 ml of water. The mixture is stirred for 4 hours at 80 C. After removing the ethanol by evaporation at reduced pressure, the mixture is acidified with HC1 (1:1) and extracted with ethyl acetate. After washing the organic extracts to neutrality and anhydrifying on Na2SO91 the solvent is evaporated under vacuum. 37.4 g of monosubstituted malonic acid are obtained.
The diacid, thus obtained, decarboxylates in 1 hour, at 160 C. 31.6 g of mono-acid are obtained.
SOC12 is added to the acid, dropwise. The mixture is stirred for 12 hours. The acyl chloride is isolated after removing the excess thionyl chloride by means of distillation under vacuum. 31.0 g of acyl chloride are obtained.
The acyl chloride dissolved in 50 ml of methylene chloride is added, at 10 C, to the suspension of A1C13 in 400 ml of methylene chloride. The mixture is stirred for 1 hour at room temperature. It is poured into ice and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated under vacuum. 22.0 g of product are obtained (total yield = 260).
O OH
NaBH4 O
22.0 g (150.7 mmoles) of 4-methyl-l-indanone 3.9 g (102.6 mmoles) of sodium boronhydride 88 ml of tetrahydrofuran 44 ml of methanol NaBH4 is added, in portions, at 0 C, to the solu-tion of 4-methyl-l-indanone in THF/CH3OH. After 3 hours the mixture is poured into water and extracted with ether. After washing the organic extracts to neutral-ity and anhydrifying on Na2SO4, the solvent is evapo-rated under vacuum. 22.0 g of 4-methyl-i-indanol are obtained (yield = 99%).
H OOEt H
o --~ o 22 g (148.6 mmoles) of 4-methyl-l-indanol 123 ml (307 mmoles) of n-butyl-lithium 2.5 M solution in hexane 750 ml of hexane 39.1 ml (322 mmoles) of diethylcarbonate N-butyl-lithium is added, at 0 C, to the solution of 4-methyl-l-indanol in hexane. The mixture is stirred for 2 hours at 60 C. Diethylcarbonate is added dropwise, at -70 C. The mixture is left to rise to room temperature. After 8 hours it is poured into water and extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated. After purification on a silica gel chromatographic column (eluant hex-ane/ethyl acetate =9/1), 6.9 g of product are obtained (yield = 21.2%) OOEt OOEt H
12.5 g (56.8 mmoles) of hydroxy ester 400 mg (2.1 mmoles) of p-toluenesulfonic acid (PTSA) 100 of toluene.
PTSA is added to the toluene solution of hydroxy ester. The mixture is stirred at boiling point, remov-ing the azeotropic mixture/toluene by distillation.
After 2 hours the mixture is washed until neutrality with a saturated solution of NaHCO3 and anhydrified on Na2SO4, and the solvent is evaporated. 10.0 g of prod-uct are thus obtained (yield = 870).
OOEt OH
LiAIH4 o --~ o 10.0 g (49.5 mmoles) of ester 1.1 g (28.9 mmoles) of lithium aluminum hydride 200 ml of ethyl ether The ester dissolved in 60 ml of ethyl ether is added, at -30 C, by means of a drip funnel, to the suspension in ethyl ether of LiAlH9. After 30 minutes water is slowly added, at 0 C, and then HC1 (2N); the mixture is extracted with ethyl ether. After washing the organic extracts __ ___-____ity and anhydrifying on Na2SOq1 the solvent is evaporated at reduced pressure.
7.8 g of alcohol are obtained (yield = 99%).
H Br O \ -~ O \
8.8 g (55 mmoles) of alcohol 1.77 ml (18.15 mmoles) of phosphorous tribromide 110 ml of inethylene chloride.
PBr3 is added dropwise, at -20 C, to the solution of alcohol in CH2C12. After 30 minutes a saturated aqueous solution of NaHCO3 is slowly added until basic pH. The mixture is extracted with ethyl ether and is washed to neutrality with water. After anhydrifying on Na2SO4 and evaporating the solvent, 7.8 g of product are obtained (yield = 64%).
Preparation of 4,7-dimethyl-indenyl-lithium O
+ ci A1C13 CH2C12 Cl H2S04 cl H; H3 14.5 g (137 mmoles) of p-xylene 16 g of A1C13 ml (104.7 mmoles) of 3-chloropropionyl chloride 5 70 ml of methylene chloride 90 ml of conc. HZS09.
A solution of 3-chloro propionyl chloride in xy-lene is dripped in about 1 hour into a suspension of A1C13 in methylene chloride maintained at 0 C in an in-10 ert atmosphere. At the end of the addition the mixture is left to rise to 10 C and is maintained at 10-20 C
for about 2 hours. It is poured into ice and extracted with methylene chloride. The organic extracts are washed with water until neutrality and then dried on sodium sulfate.
The residue obtained by evaporation of the sol-vent is added to H2SO4 at such a rate as to maintain the temperature between 20 and 30 C. At the end of the addition the mixture is brought to 80 C and maintained at this temperature for 2 hours. The mixture is then poured into ice and is extracted with ethyl ether.
ether solution is washed to neutrality with a satu-rated solution of sodium bicarbonate and then water, and is dried on sodium sulfate. The solid obtained by evaporation of the ether is washed with petroleum ether and dried. 20 g of 4,7-dimethyl-l-indanone are thus obtained (91% of yield in the two passages).
UAHH4 PT-~
0 ---~ ~ TT-IF
2.9 g (18.1 mmoles) of 4,7-dimethyl-l-indanone 0.35 g (9.2 inmoles) of LiAlH4 30 ml of ethyl ether 10 ml of THF
0.2 g (1.05 mmoles) of p-toluenesulfonic acid (PTSA).
Indanone is slowly added to the suspension of LiAlH4 maintained at -30 C in an inert atmosphere. After 30 minutes the reaction is completed. Ice and HC1 2N are carefully added, the mixture is then extracted with ethyl ether and washed to neutrality, dried on sodium sulfate and evaporated. The indanol obtained is dis-solved in 10 ml of THF, p-toluenesulfonic acid is added and the mixture is brought to reflux temperature for 1 hour. Solid NaHCO3 and Na2SO4 are added_ The mix-ture is filtered and the solvent evaporated obtaining 2.4 g of 4,7-dimethylindene (91% yield).
I,i n-BuI i O
Br 4,7-Merindenillitio 7.4 g (51.4 mmoles) of 4,7-dimethyl-indene 32.3 ml (51.6 mmoles) of LiBu 1.6 M solution in hexane 7.8 g (35.1 mmoles) of benzyl bromide 297 ml of tetrahydrofuran 148 ml of hexane LiBu is added to the solution in THF and hexane of 4,7-dimethyl-indene. After 2 hours, the bromide dissolved in 20 ml of THF and 10 ml of hexane is added, at -70 C. The mixture is left to rise to room temperature, after 8 hours water is added and the mix-ture is extracted with ethyl ether. After washing the organic extracts to neutrality and anhydrifying on Na2SO4, the solvent is evaporated. 3.1 g of product are obtained, after purification on a silica gel column using hexane/ethyl acetate as eluant in a ratio of 98/2 (yield = 310).
Synthesis of 4-methylene(2-indenyl)indene Li(N-isoPrz) Li+
O
r O
11.2 ml (79.8 mmoles) of diisopropylamine 29 ml (72.5 mmoles) of LiBu 2.5 M solution in hexane 9.5 g (72 mmoles) of 1-indanone 6.0 g (28.8 mmoles) of 4-bromethylindene LiBu is added dropwise to the solution of diiso-propylamine in 70 ml of THF, at -20 C. After 40 min-utes a 2 M solution of 1-indanone in THF is added, at -70 C. After 90 minutes a 2 M solution of 4-bromoethylindene (prepared as described in example 2) in THF is added. The mixture is left to rise to room temperature. After 30 minutes it is poured into water and extracted with ethyl ether. After washing the or-ganic extracts to neutrality, with a saturated aqueous solution of NH4C1 and with water, they are anhydrified on Na2SO4 and the solvent is evaporated. 14 g of raw 4-methylene(2-indan-l-one)indene are obtained.
NaBH4 O
OH
13.8 g of raw 4-methylene(2-indan-l-one)indene 2.6 g (68.42 mmoles) of sodium borohydride 120 ml of tetrahydrofuran 60 ml of hexane.
NaBH4 is added to the solution in THF and hexane of 1-indanone-2-substituted, at -20 C. The mixture is left to rise to room temperature. After 2 hours water is added and the mixture is extracted with ethyl ether. After washing the organic extracts to neutral-ity with a saturated aqueous solution of NH4Cl and an-hydrifying on Na2SO4, the solvent is evaporated. 13.0 g of raw 4-methylene(2-indan-l-ol)indene are obtained.
CuSO4 H
13.0 g of raw 4-methylene(2-indan-l-ol)indene 15.0 g of anhydrous copper sulfate 100 ml of toluene.
The alcohol is added to the suspension of CuSO4 in toluene. After 90 minutes at 110 C the mixture is poured into water and extracted with ethyl ether. Af-ter washing the organic extracts to neutrality with water and anhydrifying on Na2SO4, the solvent is evapo-rated. 1.8 g of 4-methylene(2-indenyl)indene are ob-tained, after purification on a silica gel column (eluant:.hexane/ethyl acetate = 99/1).
Synthesis of 1-methyl-4-methylene (1-TI5-indenyl) -r15-indenyl zirconium dichloride O O
BuLi ~Cl Zr ZrC4 ~Cl 2.4 g (9.3 mmoles) of 1-methyl-4-methylene(1-indenyl)indene cc (24 mmoles) of LiBu 1.6 M in hexane 80 cc of ethyl ether 1.7 g (5. 6 mmoles ) of ZrClq .
15 LiBu is added, by means of a drip funnel, to the ether solution of 1-methyl-4-methylene(1-indenyl)indene; approximately half-way through the ad-dition the corresponding lithium salt begins to pre-cipitate. The solution is dark yellow whereas the pre-cipitate is white. The mixture is left under stirring for a night. A DCI control (sample treated with methyl iodide) shows the presence of ligand, mono-salt and di-salt, in approximately equimolar quantities. A fur-ther 10 cc of LiBu are added. GC mass analysis reveals the presence of the di-salt with traces of mono-salt and the absence of the ligand. The mixture is left un-der stirring for 1 night.
The lithium salt is decanted, washed several times with hexane and finally dried under vacuum. The solid is suspended in about 80 cc of toluene, cooled to -70 C and then zirconium tetrachloride is added.
The temperature is left to rise spontaneously to room value and the mixture is left under stirring for a further 30 minutes. The suspension (dark red) is fil-tered and washed with toluene (3 x 10 ml) and subse-quently with methylene chloride (3 x 10 ml).
The filtrate is concentrated, the formation of pitchy products is observed, which are separated by filtration. The limpid solution is dried, and ethyl ether is added to the residue obtained. There is the initial formation of a solution from which the complex is separated in the form of a yellow solid.
1H-NMR (ppm rel. to TMS).
7.50-7.15 (m, 4H), 7.13-6.90 (m, 3H), 6.73 (d, 1H, J =
3.1 Hz) , 6.63 (d, 2H, J 2.6 Hz) , 6.54 (d, 1H, J =
3.0 Hz), 4.53 (d, 1H, J 14.0 Hz), 4.32 (d, 1H, J =
14.0 Hz), 2.44 (s, 3H).
Copolymerization of ethylene/propylene Examples 6 to 9 refer to a series of copolymeri-zation tests for the preparation of elastomeric poly-mers of the EPR type based on ethylene/propylene, car-ried out using a catalytic system comprising on the one hand the metallocene complex 1-methyl-4-methylene (1-,q5-indenyl) -rI5-indenyl zirconium dichlo-ride, obtained as described above in example 5 and methylalumoxane (MAO) as cocatalyst. The specific po-lymerization conditions of each example and the re-sults obtained are indicated in Table 1 below, which specifies in succession, the reference example number, the quantity of zirconium used, the atomic ratio be-tween aluminum in MAO and zirconium, the total polym-erization pressure, the activity of the catalytic sys-tem with reference to the zirconium, the relative quantity, by weight, of the C3 monomeric units in the polymer, the weight average molecular weight MW and the molecular weight dispersion MW/Mn.
The polymerization is carried out in a 0.5 liter pressure reactor, equipped with a magnetic anchor drag stirrer and an external jacket connected to a heat ex-changer for the temperature control. The reactor is previously flushed by maintaining under vacuum (0.1 Pascal) at a temperature of 80 C for at least 2 h.
120 g of liquid "polymerization grade" propylene are fed into the reactor at 23 C. The reactor is then brought to the polymerization temperature of 40 C and, "polymerization grade" gaseous ethylene is fed by means of a plunged pipe until the desired equilibrium pressure (2.0-2.7 MPa) is reached. Under these condi-tions the molar concentration of ethylene in the liq-uid phase ranges from 11 to 23%, depending on the to-tal pressure of the system, as can be easily calcu-lated using the appropriate liquid-vapor tables.
MAO, as a 1.5 M solution (as Al) in toluene (com-mercial product Eurecene 5100 10T of Witco) and the desired quantity of the above metallocene complex, as a toluene solution having a concentration generally ranging from 3 x 10-4 to 1 x 10-3 M, are charged into a suitable tailed test-tube, maintained under nitrogen.
The catalyst solution thus formed is maintained at room temperature for a few minutes and is then trans-ferred under a stream of inert gas to a metal con-tainer from which it is introduced into the reactor, by means of an overpressure of nitrogen.
The polymerization reaction is carried out at 40 C, care being taken that the total pressure is kept constant by continuously feeding ethylene to compen-sate the part which has reacted in the meantime. After 15 minutes the feeding of ethylene is interrupted and the polymerization is stopped by the rapid degassing of the residual monomers. The polymer is recovered, after washing it with ethyl alcohol and drying at 60 C, 1000 Pa, for at least 8 h. The solid thus ob-tained is weighed and the catalytic activity is calcu-lated as kilograms of polymer per gram of metal zirco-nium per hour: (kgPo,./gzrxh) . The content of the pro-pylene units is measured on the dried and homogenized solid, by means of the known techniques based on IR
spectroscopy, together with the weight (Mw) and number (Mn) average molecular weight. The results are indi-cated in Table 1.
Examples 10 to 12 refer to a series of copolym-erization tests for the preparation of elastomeric polymers of the EPR type based on ethylene/propylene using a catalytic system comprising the metallocene complex, obtained as described above in example 5, an aluminum alkyl and an appropriate compound of boron as cocatalyst.
The procedure described in examples 6-9 is fol-lowed with the following variations:
About 120 g of "polymerization grade" liquid pro-pylene and the exact quantity of A1(iso-Bu)3 are fed into the reactor at 23 C, so as to obtain a concentra-tion of aluminum equal to 5 x 10-3 moles/liter. The re-actor is then brought to the polymerization tempera-ture of 40 C and "polymerization grade" gaseous ethyl-ene is fed by means of a plunged pipe, until the de-sired equilibrium pressure (2.2-2.7 MPa) is reached.
Under these conditions the molar concentration of eth-ylene in the liquid phase ranges from 12 to 23%, de-pending on the total pressure of the system, as can be easily calculated using the appropriate liquid-vapor tables.
Al(iso-Bu)3 as an 0.4 M solution in toluene and the desired quantity of metallocene complex, prepared as described in example 5, as a toluene solution hav-ing a concentration generally ranging from 3 x 10-4 to 1 x 10-3 M, are charged into a suitable tailed test-tube, maintained under nitrogen. The solution thus ob-tained is maintained under stirring at 23 C for 15 minutes after which a toluene solution, having a con-centration generally ranging from 5 x 10-4 to 1 x 10-3 M, of [CPh3] [B (C6F5) 4] is added and, after a few min-utes, it is transferred under a stream of inert gas to a metal container from which it is introduced into the reactor, by means of an overpressure of nitrogen.
The results are indicated in Table 2.
~ _ >1 Co rn ~ (N
\ . . . .
N N N N
O
OD [-'-1 3 O ~ ( 7 (D
U) ~)4 o~
N
~ E 41 Un KT Ol ~ ~ 0 Cl C0 U=) (~') r-I
U) U ~
U
-r-I ~(S
>1 N
~ O >1 k =rI
.~ J ~ ~ t, 00 ~ ~ O
(d 0 _~ ri O N O
U -P N OD
~ l0 U ~ tai 41 N Lo t-~ O p., . . . .
4J ~4 a x (N (N N (N
U) -=-1 (D N
O ~-_:
.-i N 4 0 Ur) LO O O
l- OD LO CO
\ \ Ol (,=) Ql Ol ln ~4 a) r--I
O uO O Ln co =
U .{ U) l- M lfl M
r1 N a) .
~ O. O
U r+
4) 4) ~
rn >1 OD
ri x H ~ W
\ . .
~ ~ C'') N N
a ~ np N [~ O
O ko (n Q X r1 N l`') O
U
O
t4Jl) l-1 >1 00 -4 Ln U) r1 0 =r-I
U `o ~
~ u 4J
>1 H
c~
41 ~4 0 >' k +J
U ~ =r-I oD Ol ~ U 110 u) ~ -H
LO
~ - I N
-~} J--~ 0 X~ tD) U) -r-I
O
41 U ~ (d N LC) r-f7 O a = = =
O -ri a N N
N
~
ri rl ^
-I >1 U O N
r-I r-I f-I .-i -J:., m u) O
U) LO
N
O >1 S-I 0 -i ~:: N r, O O (D
41 \ ff) LO if) RS r-I r I (Y) l=) (Y) -~
LO
N
O C) 0, -4 O ~ >C .-1 Ol U N u) . . .
a) .-i O o U -i 41 O~.+N
r ' ~ v V
N a) a) >1 44io ~' O r-I N
~(Il U ~ z a) x Ln
NaBH4 O
OH
13.8 g of raw 4-methylene(2-indan-l-one)indene 2.6 g (68.42 mmoles) of sodium borohydride 120 ml of tetrahydrofuran 60 ml of hexane.
NaBH4 is added to the solution in THF and hexane of 1-indanone-2-substituted, at -20 C. The mixture is left to rise to room temperature. After 2 hours water is added and the mixture is extracted with ethyl ether. After washing the organic extracts to neutral-ity with a saturated aqueous solution of NH4Cl and an-hydrifying on Na2SO4, the solvent is evaporated. 13.0 g of raw 4-methylene(2-indan-l-ol)indene are obtained.
CuSO4 H
13.0 g of raw 4-methylene(2-indan-l-ol)indene 15.0 g of anhydrous copper sulfate 100 ml of toluene.
The alcohol is added to the suspension of CuSO4 in toluene. After 90 minutes at 110 C the mixture is poured into water and extracted with ethyl ether. Af-ter washing the organic extracts to neutrality with water and anhydrifying on Na2SO4, the solvent is evapo-rated. 1.8 g of 4-methylene(2-indenyl)indene are ob-tained, after purification on a silica gel column (eluant:.hexane/ethyl acetate = 99/1).
Synthesis of 1-methyl-4-methylene (1-TI5-indenyl) -r15-indenyl zirconium dichloride O O
BuLi ~Cl Zr ZrC4 ~Cl 2.4 g (9.3 mmoles) of 1-methyl-4-methylene(1-indenyl)indene cc (24 mmoles) of LiBu 1.6 M in hexane 80 cc of ethyl ether 1.7 g (5. 6 mmoles ) of ZrClq .
15 LiBu is added, by means of a drip funnel, to the ether solution of 1-methyl-4-methylene(1-indenyl)indene; approximately half-way through the ad-dition the corresponding lithium salt begins to pre-cipitate. The solution is dark yellow whereas the pre-cipitate is white. The mixture is left under stirring for a night. A DCI control (sample treated with methyl iodide) shows the presence of ligand, mono-salt and di-salt, in approximately equimolar quantities. A fur-ther 10 cc of LiBu are added. GC mass analysis reveals the presence of the di-salt with traces of mono-salt and the absence of the ligand. The mixture is left un-der stirring for 1 night.
The lithium salt is decanted, washed several times with hexane and finally dried under vacuum. The solid is suspended in about 80 cc of toluene, cooled to -70 C and then zirconium tetrachloride is added.
The temperature is left to rise spontaneously to room value and the mixture is left under stirring for a further 30 minutes. The suspension (dark red) is fil-tered and washed with toluene (3 x 10 ml) and subse-quently with methylene chloride (3 x 10 ml).
The filtrate is concentrated, the formation of pitchy products is observed, which are separated by filtration. The limpid solution is dried, and ethyl ether is added to the residue obtained. There is the initial formation of a solution from which the complex is separated in the form of a yellow solid.
1H-NMR (ppm rel. to TMS).
7.50-7.15 (m, 4H), 7.13-6.90 (m, 3H), 6.73 (d, 1H, J =
3.1 Hz) , 6.63 (d, 2H, J 2.6 Hz) , 6.54 (d, 1H, J =
3.0 Hz), 4.53 (d, 1H, J 14.0 Hz), 4.32 (d, 1H, J =
14.0 Hz), 2.44 (s, 3H).
Copolymerization of ethylene/propylene Examples 6 to 9 refer to a series of copolymeri-zation tests for the preparation of elastomeric poly-mers of the EPR type based on ethylene/propylene, car-ried out using a catalytic system comprising on the one hand the metallocene complex 1-methyl-4-methylene (1-,q5-indenyl) -rI5-indenyl zirconium dichlo-ride, obtained as described above in example 5 and methylalumoxane (MAO) as cocatalyst. The specific po-lymerization conditions of each example and the re-sults obtained are indicated in Table 1 below, which specifies in succession, the reference example number, the quantity of zirconium used, the atomic ratio be-tween aluminum in MAO and zirconium, the total polym-erization pressure, the activity of the catalytic sys-tem with reference to the zirconium, the relative quantity, by weight, of the C3 monomeric units in the polymer, the weight average molecular weight MW and the molecular weight dispersion MW/Mn.
The polymerization is carried out in a 0.5 liter pressure reactor, equipped with a magnetic anchor drag stirrer and an external jacket connected to a heat ex-changer for the temperature control. The reactor is previously flushed by maintaining under vacuum (0.1 Pascal) at a temperature of 80 C for at least 2 h.
120 g of liquid "polymerization grade" propylene are fed into the reactor at 23 C. The reactor is then brought to the polymerization temperature of 40 C and, "polymerization grade" gaseous ethylene is fed by means of a plunged pipe until the desired equilibrium pressure (2.0-2.7 MPa) is reached. Under these condi-tions the molar concentration of ethylene in the liq-uid phase ranges from 11 to 23%, depending on the to-tal pressure of the system, as can be easily calcu-lated using the appropriate liquid-vapor tables.
MAO, as a 1.5 M solution (as Al) in toluene (com-mercial product Eurecene 5100 10T of Witco) and the desired quantity of the above metallocene complex, as a toluene solution having a concentration generally ranging from 3 x 10-4 to 1 x 10-3 M, are charged into a suitable tailed test-tube, maintained under nitrogen.
The catalyst solution thus formed is maintained at room temperature for a few minutes and is then trans-ferred under a stream of inert gas to a metal con-tainer from which it is introduced into the reactor, by means of an overpressure of nitrogen.
The polymerization reaction is carried out at 40 C, care being taken that the total pressure is kept constant by continuously feeding ethylene to compen-sate the part which has reacted in the meantime. After 15 minutes the feeding of ethylene is interrupted and the polymerization is stopped by the rapid degassing of the residual monomers. The polymer is recovered, after washing it with ethyl alcohol and drying at 60 C, 1000 Pa, for at least 8 h. The solid thus ob-tained is weighed and the catalytic activity is calcu-lated as kilograms of polymer per gram of metal zirco-nium per hour: (kgPo,./gzrxh) . The content of the pro-pylene units is measured on the dried and homogenized solid, by means of the known techniques based on IR
spectroscopy, together with the weight (Mw) and number (Mn) average molecular weight. The results are indi-cated in Table 1.
Examples 10 to 12 refer to a series of copolym-erization tests for the preparation of elastomeric polymers of the EPR type based on ethylene/propylene using a catalytic system comprising the metallocene complex, obtained as described above in example 5, an aluminum alkyl and an appropriate compound of boron as cocatalyst.
The procedure described in examples 6-9 is fol-lowed with the following variations:
About 120 g of "polymerization grade" liquid pro-pylene and the exact quantity of A1(iso-Bu)3 are fed into the reactor at 23 C, so as to obtain a concentra-tion of aluminum equal to 5 x 10-3 moles/liter. The re-actor is then brought to the polymerization tempera-ture of 40 C and "polymerization grade" gaseous ethyl-ene is fed by means of a plunged pipe, until the de-sired equilibrium pressure (2.2-2.7 MPa) is reached.
Under these conditions the molar concentration of eth-ylene in the liquid phase ranges from 12 to 23%, de-pending on the total pressure of the system, as can be easily calculated using the appropriate liquid-vapor tables.
Al(iso-Bu)3 as an 0.4 M solution in toluene and the desired quantity of metallocene complex, prepared as described in example 5, as a toluene solution hav-ing a concentration generally ranging from 3 x 10-4 to 1 x 10-3 M, are charged into a suitable tailed test-tube, maintained under nitrogen. The solution thus ob-tained is maintained under stirring at 23 C for 15 minutes after which a toluene solution, having a con-centration generally ranging from 5 x 10-4 to 1 x 10-3 M, of [CPh3] [B (C6F5) 4] is added and, after a few min-utes, it is transferred under a stream of inert gas to a metal container from which it is introduced into the reactor, by means of an overpressure of nitrogen.
The results are indicated in Table 2.
~ _ >1 Co rn ~ (N
\ . . . .
N N N N
O
OD [-'-1 3 O ~ ( 7 (D
U) ~)4 o~
N
~ E 41 Un KT Ol ~ ~ 0 Cl C0 U=) (~') r-I
U) U ~
U
-r-I ~(S
>1 N
~ O >1 k =rI
.~ J ~ ~ t, 00 ~ ~ O
(d 0 _~ ri O N O
U -P N OD
~ l0 U ~ tai 41 N Lo t-~ O p., . . . .
4J ~4 a x (N (N N (N
U) -=-1 (D N
O ~-_:
.-i N 4 0 Ur) LO O O
l- OD LO CO
\ \ Ol (,=) Ql Ol ln ~4 a) r--I
O uO O Ln co =
U .{ U) l- M lfl M
r1 N a) .
~ O. O
U r+
4) 4) ~
rn >1 OD
ri x H ~ W
\ . .
~ ~ C'') N N
a ~ np N [~ O
O ko (n Q X r1 N l`') O
U
O
t4Jl) l-1 >1 00 -4 Ln U) r1 0 =r-I
U `o ~
~ u 4J
>1 H
c~
41 ~4 0 >' k +J
U ~ =r-I oD Ol ~ U 110 u) ~ -H
LO
~ - I N
-~} J--~ 0 X~ tD) U) -r-I
O
41 U ~ (d N LC) r-f7 O a = = =
O -ri a N N
N
~
ri rl ^
-I >1 U O N
r-I r-I f-I .-i -J:., m u) O
U) LO
N
O >1 S-I 0 -i ~:: N r, O O (D
41 \ ff) LO if) RS r-I r I (Y) l=) (Y) -~
LO
N
O C) 0, -4 O ~ >C .-1 Ol U N u) . . .
a) .-i O o U -i 41 O~.+N
r ' ~ v V
N a) a) >1 44io ~' O r-I N
~(Il U ~ z a) x Ln
Claims (34)
1. A metallocene compound having formula (I):
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
2. The metallocene compound of claim 1, wherein the halogen is selected from the group consisting of F, Cl and Br.
3. The metallocene compound of claim 1 or 2, wherein the heteroatom is selected from the group consisting of Si, O, N, S and P.
4. A metallocene compound having formula (I):
wherein R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal;
M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M, wherein groups X1 and X2 are selected from chloride, methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, allyl, methylallyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, toluyl, methoxyl, ethoxyl, iso-butoxyl, sec-butoxyl, ethylsulfide, acetate, propionate, butyrate, pivalate, versatate, naphthenate, diethylamide, dibutylamide, or bis(trimethylsilyl)amide; or wherein X1 and X2 are chemically bound to each other to form one or more divalent anionic groups.
wherein R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal;
M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M, wherein groups X1 and X2 are selected from chloride, methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, allyl, methylallyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, toluyl, methoxyl, ethoxyl, iso-butoxyl, sec-butoxyl, ethylsulfide, acetate, propionate, butyrate, pivalate, versatate, naphthenate, diethylamide, dibutylamide, or bis(trimethylsilyl)amide; or wherein X1 and X2 are chemically bound to each other to form one or more divalent anionic groups.
5. The metallocene compound of claim 4, wherein the divalent anionic group is a trimethylene, tetramethylene or ethylenedioxy group.
6. The metallocene compound of claim 4 or 5, wherein the halogen is selected from the group consisting of F, Cl and Br.
7. The metallocene compound of any one of claims 4 to 6, wherein the heteroatom is selected from the group consisting of Si, O, N, S and P.
8. A compound having formula (Ia):
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms.
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms.
9. The compound according to claim 8, selected from the group consisting of:
10. The compound of claim 8, wherein the halogen is selected from the group consisting of F, Cl and Br.
11. The metallocene compound of claim 8 or 9, wherein the heteroatom of Groups 14-16 of the periodic table of the elements is selected from the group consisting of Si, O, N, S and P.
12. A process for the preparation of the compound (Ia) comprising:
(a) reaction of 1-indanol derivatives having formula (II), with LiBu to give the double salt having formula (III):
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group, and R1, R2, R3, R4, R5, R6, R7, and R8 may independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
(b) reaction of the double lithium salt having formula (III), obtained in (a), with one or more electrophilic reagents, to obtain hydroxy ester (IV);
(c) dehydration reaction of the alcohol function of the hydroxy ester (IV), obtained in (b), carried out in an acid environment to give the ester (V);
(d) reduction reaction of the ester having formula (V), obtained in (c), with the formation of alcohol (VI):
(e) bromination reaction of the alcohol having formula (VI) to give the bromine derivative (VII):
(f) formation reaction of the indenyl cyclopentadienyl derivative having formula (Ia), starting from the bromine derivative having formula (VII) obtained in (e) and from cyclopentadienyl anions, whose corresponding neutral derivative can be represented by the following formula (VIII):
(a) reaction of 1-indanol derivatives having formula (II), with LiBu to give the double salt having formula (III):
wherein:
R1 and R2 can independently occupy any of the free positions of the indene group, and R1, R2, R3, R4, R5, R6, R7, and R8 may independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements, wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
(b) reaction of the double lithium salt having formula (III), obtained in (a), with one or more electrophilic reagents, to obtain hydroxy ester (IV);
(c) dehydration reaction of the alcohol function of the hydroxy ester (IV), obtained in (b), carried out in an acid environment to give the ester (V);
(d) reduction reaction of the ester having formula (V), obtained in (c), with the formation of alcohol (VI):
(e) bromination reaction of the alcohol having formula (VI) to give the bromine derivative (VII):
(f) formation reaction of the indenyl cyclopentadienyl derivative having formula (Ia), starting from the bromine derivative having formula (VII) obtained in (e) and from cyclopentadienyl anions, whose corresponding neutral derivative can be represented by the following formula (VIII):
13. The process according to claim 12, wherein:
(a) is carried out in an organic solvent, in the presence of one or more base reagents and at temperatures of from -30° to 120°C;
(b) is carried out in the presence of hydrocarbon and/or ether solvents or mixtures thereof at temperatures of from -100° to 120°C;
(c) is carried out in the presence of a solvent and a strong acid at temperatures of from -25° to 150°C;
(d) is carried out in an organic solvent, with a reagent selected from the group consisting of LiAlH4, NaBH4, NaH, MgH2, LiBu, LiMe, MeMgCl, PhMgBr, and Bu t MgCl at temperatures of from -70° to 100°C;
(e) is carried out in an organic solvent by means of a brominating agent;
(f) is carried out in a solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, ethers and mixtures thereof, at a temperature of from -80° to 120°C. and the cyclopentadienyl anion is obtained by the reaction of the corresponding neutral derivative, having formula (VIII), with a reagent selected from the group consisting of alkyls of electro-positive metals, hydrides of electro-positive metals, Grignard reagents, alkaline metals, earth-alkaline metals and alloys of alkaline and earth-alkaline metals, in a solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ethers and mixtures thereof, at temperatures of from -80°
to 110°C.
(a) is carried out in an organic solvent, in the presence of one or more base reagents and at temperatures of from -30° to 120°C;
(b) is carried out in the presence of hydrocarbon and/or ether solvents or mixtures thereof at temperatures of from -100° to 120°C;
(c) is carried out in the presence of a solvent and a strong acid at temperatures of from -25° to 150°C;
(d) is carried out in an organic solvent, with a reagent selected from the group consisting of LiAlH4, NaBH4, NaH, MgH2, LiBu, LiMe, MeMgCl, PhMgBr, and Bu t MgCl at temperatures of from -70° to 100°C;
(e) is carried out in an organic solvent by means of a brominating agent;
(f) is carried out in a solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, ethers and mixtures thereof, at a temperature of from -80° to 120°C. and the cyclopentadienyl anion is obtained by the reaction of the corresponding neutral derivative, having formula (VIII), with a reagent selected from the group consisting of alkyls of electro-positive metals, hydrides of electro-positive metals, Grignard reagents, alkaline metals, earth-alkaline metals and alloys of alkaline and earth-alkaline metals, in a solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ethers and mixtures thereof, at temperatures of from -80°
to 110°C.
14. The process according to claim 13, wherein:
(a) is carried out in hexane as solvent, in the presence of lithium butyl at temperatures of from 0° to 70°C;
(b) is carried out in hexane as solvent at temperatures of from -70° to 25°C;
(c) is carried out in toluene as solvent in the presence of para-toluenesulfonic acid, at temperatures of from 50° to 110°C;
(d) is carried out in ethyl ether, in the presence of LiAlH4, at temperatures of from -30° to 25°C;
(e) is carried out in methylene chloride in the presence of PBr3 at temperatures of from -20° to 25°C;
(f) the cyclopentadienyl anion is obtained by the reaction between indene or 4,7-dimethyl-indene, with lithium butyl, in mixtures of hexane/THF at temperatures of from 0° to 60°C.
(a) is carried out in hexane as solvent, in the presence of lithium butyl at temperatures of from 0° to 70°C;
(b) is carried out in hexane as solvent at temperatures of from -70° to 25°C;
(c) is carried out in toluene as solvent in the presence of para-toluenesulfonic acid, at temperatures of from 50° to 110°C;
(d) is carried out in ethyl ether, in the presence of LiAlH4, at temperatures of from -30° to 25°C;
(e) is carried out in methylene chloride in the presence of PBr3 at temperatures of from -20° to 25°C;
(f) the cyclopentadienyl anion is obtained by the reaction between indene or 4,7-dimethyl-indene, with lithium butyl, in mixtures of hexane/THF at temperatures of from 0° to 60°C.
15. The process of claim 13, wherein the strong acid is selected from the group consisting of HCl, H2SO4, para-toluenesulfonic acid and a blander dehydrating agent.
16. The process of claim 15, wherein the blander dehydrating agent is a silica gel.
17. The process according to claim 12, wherein (f) is carried out by reacting the brominated product (VII) with a lithium enolate to form one or more indenyl-cyclopentadienyl products having formula (XIII):
wherein:
R1 and R2 can independently occupy any of the free positions of the indenyl group;
R1, R2, R7, R8, R9, R10, and R11 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; or, wherein any two of the substituents R9, R10 and R11, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
R12 can be independently hydrogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements;
said process further comprising:
(g) reaction of a cyclic ketone having formula (IX), with a lithium amide to form a mixture of one or more anions having formula (Xa)/(Xb):
(h) reaction of the mixture of anions (Xa)/(Xb) with the brominated product having formula (VII), prepared according to (g) to form (XI):
(i) reduction of the functional carbonyl group to alcohol with the formation of the derivative having formula (XII):
(j) dehydration of the derivative having formula (XII), obtained in (i), with the formation of the indenyl-cyclopentadienyl compound, having formula (XIII).
wherein:
R1 and R2 can independently occupy any of the free positions of the indenyl group;
R1, R2, R7, R8, R9, R10, and R11 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements; or, wherein any two of the substituents R9, R10 and R11, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
R12 can be independently hydrogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C1-C20 hydrocarbyl group, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements;
said process further comprising:
(g) reaction of a cyclic ketone having formula (IX), with a lithium amide to form a mixture of one or more anions having formula (Xa)/(Xb):
(h) reaction of the mixture of anions (Xa)/(Xb) with the brominated product having formula (VII), prepared according to (g) to form (XI):
(i) reduction of the functional carbonyl group to alcohol with the formation of the derivative having formula (XII):
(j) dehydration of the derivative having formula (XII), obtained in (i), with the formation of the indenyl-cyclopentadienyl compound, having formula (XIII).
18. The process of claim 17, wherein the halogen is selected from the group consisting of F, Cl and Br.
19. The process of claim 17 or 18, wherein the heteroatom is selected from the group consisting of Si, O, N, S and P.
20. The process of claim 12, wherein the electrophilic reagent is diethyl carbonate.
21. The process of claim 12 or 20, wherein the halogen is selected from the group consisting of F, Cl and Br.
22. The process of any one of claims 12, 20 and 21, wherein the heteroatom is selected from the group consisting of Si, O, N, S and P.
23. The process according to any one of claims 12, 20, 21 and 22, wherein the cyclopentadienyl anion is obtained by the reaction of the corresponding neutral derivative, having formula (VIII), with a reagent selected from the group consisting of alkyls of lithium, lithium hydride and lithium metal.
24. A catalyst for the polymerization of olefins comprising a reaction product between:
(A) one or more metallocene compounds having formula (I), free or supported on inert solids; and (B) one or more compounds capable of forming a metallocene alkyl cation, wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C20 hydrocarbyl group, or a C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements;
wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
(A) one or more metallocene compounds having formula (I), free or supported on inert solids; and (B) one or more compounds capable of forming a metallocene alkyl cation, wherein:
R1 and R2 can independently occupy any of the free positions of the indene group;
R1, R2, R3, R4, R5, R6, R7 and R8 independently represent hydrogen, halogen, a linear or branched, saturated or unsaturated, cycloaliphatic or aromatic C20 hydrocarbyl group, or a C20 hydrocarbyl group substituted with one or more halogen atoms, or a C1-C20 hydrocarbyl group comprising one or more heteroatoms of groups 14 to 16 of the periodic table of elements;
wherein any two, or both pairs, of the substituents R3, R4, R5 and R6, adjacent to each other, may be joined to each other to form a saturated or unsaturated C4-C20 cyclic structure, said structure optionally containing one or more heteroatoms;
M represents titanium, zirconium or hafnium;
X1 and X2 each independently represent an anionic group bound to the metal M, wherein X1 and X2 may be chemically bound to each other to form a cycle having from 4 to 7 atoms different from hydrogen, also comprising the metal M.
25. The catalyst for the polymerization of olefins according to claim 24, wherein the compound B is an aluminoxane.
26. The catalyst of claim 24 or 25, wherein the halogen is selected from the group consisting of F, Cl and Br.
27. The catalyst of any one of claims 24 to 26, wherein the heteroatom is selected from the group consisting of Si, O, N, S and P.
28. A process for the preparation of the catalyst according to claim 24, comprising: contacting the components (A) and (B) with each other at temperatures of from 200 to 60°C. and for times from 10 seconds to 1 hour, in a hydrocarbon medium and in a proportion that the atomic ratio between the aluminum in the aluminoxane and the transition metal M is within the range of to 10000.
29. The process of claim 25, wherein the atomic ratio between the aluminum in the alumoxane and the transition metal M is from 100 to 5,000.
30. A process for the polymerization of olefins, comprising polymerizing one or more olefinic monomers in the presence of the catalyst as defined in any one of claims 25 to 27.
31. The process according to claim 3O, wherein one or more olefinic monomers are polymerized in the presence of a metallocene having formula (I) and methylalumoxane (MAO) as a cocatalyst.
32. The process according to claim 31, wherein the olefinic monomers are polymerized in the presence of a metallocene having formula (I), an aluminum alkyl and a boron compound as a cocatalyst.
33. The process according to claim 32, wherein the olefinic monomers are selected from the group consisting of ethylene, propylene and mixtures thereof.
34. The process of claim 31, wherein the olefinic monomers are selected from the group consisting of ethylene, propylene and mixtures thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI99A002536 | 1999-12-03 | ||
| IT1999MI002536A IT1314261B1 (en) | 1999-12-03 | 1999-12-03 | METALLOCENIC COMPOUNDS BRIDGE, PROCESS FOR THEIR PREPARATION AND THEIR USE AS CATALYSTS FOR THE POLYMERIZATION OF OLEFINS. |
| PCT/EP2000/011824 WO2001040238A1 (en) | 1999-12-03 | 2000-11-27 | Bridged metallocene compounds as olefin-polymerization catalysts |
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| CA2393175C true CA2393175C (en) | 2009-01-27 |
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| EP (1) | EP1250342B1 (en) |
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| TW200420573A (en) | 2002-09-26 | 2004-10-16 | Rib X Pharmaceuticals Inc | Bifunctional heterocyclic compounds and methods of making and using same |
| EP2716647A3 (en) | 2004-02-27 | 2014-08-20 | Rib-X Pharmaceuticals, Inc. | Macrocyclic compounds and methods of making and using the same |
| EP2215129A2 (en) * | 2007-08-27 | 2010-08-11 | Borealis Technology OY | Catalysts |
| EP2223944A1 (en) | 2009-02-26 | 2010-09-01 | Borealis AG | Process for producing semicrystalline propylene polymers |
| WO2011021805A2 (en) | 2009-08-18 | 2011-02-24 | 주식회사 엘지화학 | Novel compound, catalyst composition comprising same, and method for preparing a cyclic olefin polymer using same |
| JP6036108B2 (en) * | 2012-03-29 | 2016-11-30 | 日本ポリエチレン株式会社 | Process for producing ethylene polymer |
| KR101760494B1 (en) * | 2014-12-12 | 2017-07-21 | 주식회사 엘지화학 | Metallocene supported catalyst and method for preparing polyolefin using the same |
| WO2017095079A1 (en) * | 2015-12-04 | 2017-06-08 | 주식회사 엘지화학 | Method for preparing supported hybrid metallocene catalyst , and supported hybrid metallocene catalyst prepared using same |
| CN108383862B (en) * | 2018-02-08 | 2021-03-30 | 中国石油天然气股份有限公司 | Indeno [2,1-b ] indolyl rare earth metal complex and preparation method thereof |
| EP3802644A4 (en) | 2018-06-04 | 2021-08-18 | ExxonMobil Chemical Patents Inc. | Metallocenes with si-si bridges |
| US11198747B2 (en) | 2018-06-04 | 2021-12-14 | Exxonmobil Chemical Patents Inc. | Catalyst systems including two hafnocene catalyst compounds |
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| US5451649A (en) * | 1991-05-09 | 1995-09-19 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
| NL9201970A (en) * | 1992-11-11 | 1994-06-01 | Dsm Nv | Indenyl compounds and catalyst components for the polymerization of olefins. |
| DE69431222T2 (en) * | 1993-06-07 | 2003-04-17 | Mitsui Chemicals Inc | Transition metal compound, and polymerization catalyst containing the same |
| JPH11503379A (en) * | 1995-04-11 | 1999-03-26 | ダブリュ．エル．ゴア．アンド アソシエイツ，インコーポレイティド | Infrared reflective coating |
| IT1275408B (en) * | 1995-05-30 | 1997-08-05 | Spherilene Spa | BIS-INDENYL METALLOCENIC COMPOUNDS PONTANTS PROCEDURE FOR THEIR PREPARATION AND THEIR USE IN CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| DE19546501A1 (en) * | 1995-12-13 | 1997-06-19 | Hoechst Ag | Metallocene compound |
| US5780659A (en) * | 1996-03-29 | 1998-07-14 | Phillips Petroleum Company | Substituted indenyl unbridged metallocenes |
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